CN113039177A - Material for forming film for lithography, composition for forming film for lithography, underlayer film for lithography, and pattern formation method - Google Patents

Material for forming film for lithography, composition for forming film for lithography, underlayer film for lithography, and pattern formation method Download PDF

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Publication number
CN113039177A
CN113039177A CN201980075418.XA CN201980075418A CN113039177A CN 113039177 A CN113039177 A CN 113039177A CN 201980075418 A CN201980075418 A CN 201980075418A CN 113039177 A CN113039177 A CN 113039177A
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film
forming
lithography
group
mass
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山根正大
山田弘一
堀内淳矢
牧野岛高史
越后雅敏
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Mitsubishi Gas Chemical Co Inc
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Mitsubishi Gas Chemical Co Inc
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/44—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members
    • C07D207/444—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members having two doubly-bound oxygen atoms directly attached in positions 2 and 5
    • C07D207/448—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members having two doubly-bound oxygen atoms directly attached in positions 2 and 5 with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms, e.g. maleimide
    • C07D207/452—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members having two doubly-bound oxygen atoms directly attached in positions 2 and 5 with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms, e.g. maleimide with hydrocarbon radicals, substituted by hetero atoms, directly attached to the ring nitrogen atom
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/02—Polyamines
    • C08G73/0233—Polyamines derived from (poly)oxazolines, (poly)oxazines or having pendant acyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/12—Unsaturated polyimide precursors
    • C08G73/123—Unsaturated polyimide precursors the unsaturated precursors comprising halogen-containing substituents
    • C—CHEMISTRY; METALLURGY
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/12—Unsaturated polyimide precursors
    • C08G73/126—Unsaturated polyimide precursors the unsaturated precursors being wholly aromatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/12—Unsaturated polyimide precursors
    • C08G73/126—Unsaturated polyimide precursors the unsaturated precursors being wholly aromatic
    • C08G73/127—Unsaturated polyimide precursors the unsaturated precursors being wholly aromatic containing oxygen in the form of ether bonds in the main chain
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0025—Crosslinking or vulcanising agents; including accelerators
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08L79/085—Unsaturated polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
    • C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C09D179/085—Unsaturated polyimide precursors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/075—Silicon-containing compounds
    • G03F7/0752—Silicon-containing compounds in non photosensitive layers or as additives, e.g. for dry lithography
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/094—Multilayer resist systems, e.g. planarising layers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/16—Coating processes; Apparatus therefor
    • G—PHYSICS
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    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
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    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
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    • H—ELECTRICITY
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    • H01L21/0273—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers characterised by the treatment of photoresist layers
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Abstract

The present invention provides a film-forming material for lithography, comprising: a compound having a group of the formula (0A) and a group of the formula (0B) (in the formula (0B), R is each independently selected from a hydrogen atom and carbonA number of 1 to 4 alkyl groups. Wherein at least one R is an alkyl group having 1 to 4 carbon atoms. ).

Description

Material for forming film for lithography, composition for forming film for lithography, underlayer film for lithography, and pattern formation method
Technical Field
The present invention relates to a material for forming a film for lithography, a composition for forming a film for lithography containing the material, an underlayer film for lithography formed using the composition, and a pattern forming method (for example, a resist pattern method or a circuit pattern method) using the composition.
Background
In the manufacture of semiconductor devices, microfabrication is performed by photolithography using a photoresist material. In recent years, with the high integration and high speed of LSIs, further miniaturization based on pattern rules has been demanded. Moreover, in photolithography using light exposure, which is now used as a general technique, the limit of intrinsic resolution derived from the wavelength of a light source is increasingly approached.
A light source for lithography used for forming a resist pattern has a shorter wavelength from KrF excimer laser (248nm) to ArF excimer laser (193 nm). However, as the miniaturization of the resist pattern progresses, a problem of resolution or a problem of collapse of the resist pattern after development arises, and therefore, thinning of the resist is expected. However, when only the resist is thinned, it is difficult to obtain a sufficient thickness of the resist pattern in the substrate processing. Therefore, a process is necessary in which not only a resist pattern but also a resist underlayer film is formed between a resist and a semiconductor substrate to be processed, and the resist underlayer film is made to function as a mask in processing the substrate.
Various resist underlayer films are known as resist underlayer films for such processes. For example, as a material for realizing a resist underlayer film for lithography having a selection ratio close to the dry etching rate of a resist, which is different from a conventional resist underlayer film having a high etching rate, a multilayer resist process underlayer film forming material containing a resin component having at least a substituent group which generates a sulfonic acid residue by removing a terminal group by applying a predetermined energy and a solvent has been proposed (see patent document 1). As a material for realizing a resist underlayer film for lithography having a selection ratio of a dry etching rate smaller than that of a resist, a resist underlayer film material containing a polymer having a specific repeating unit has been proposed (see patent document 2). Further, as a material for realizing a resist underlayer film for lithography having a selection ratio of a dry etching rate lower than that of a semiconductor substrate, a resist underlayer film material containing a polymer obtained by copolymerizing an acenaphthylene-based repeating unit and a repeating unit having a substituted or unsubstituted hydroxyl group has been proposed (see patent document 3).
On the other hand, as a material having high etching resistance in such a resist underlayer film, an amorphous carbon underlayer film formed by CVD using methane gas, ethane gas, acetylene gas, or the like as a raw material is known.
Further, the present inventors have proposed a lower layer film forming composition for lithography containing a naphthalene formaldehyde polymer containing a specific structural unit and an organic solvent as a material which is excellent in optical properties and etching resistance, soluble in a solvent and applicable to a wet process (see patent documents 4 and 5).
As a method for forming an intermediate layer used for forming a resist underlayer film in a 3-layer process, for example, a method for forming a silicon nitride film (see patent document 6) and a method for forming a silicon nitride film by CVD (see patent document 7) are known. As an interlayer material for a 3-layer process, a material containing a silsesquioxane-based silicon compound is known (see patent documents 8 and 9).
Patent document 10 discloses a photosensitive resin composition containing (a) an alkali-soluble binder polymer, (B) a photopolymerizable compound, (C) a photopolymerization initiator, and (D) a maleic acid derivative, and one of (D) maleic acid derivatives is polymaleimide represented by formula (5 a). The photosensitive resin composition is reported to be excellent in all of sensitivity, resolution, and adhesion to a substrate.
Figure BDA0003066334200000021
[ in the formula, R51Represents a single bond, a 2-valent organic group consisting of at least 1 group selected from the group consisting of alkylene, arylene, oxy, carbonyl, ester, carbonate and carbamate, and R91And R92Each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group, an alkoxy group or a halogen atom, and q is 1 to (R)51Number of atomic bonds capable of bonding), and further, R91And R92Optionally incorporated with the carbons at positions 3 and 4 of the imide group to form a 2-valent group that constitutes a 5-or 6-membered ring structure.]
Patent document 11 discloses a resin composition containing a cyanate ester compound (a) and a bismaleimide compound (B) represented by the following formula (1), which can realize a printed wiring board excellent in heat resistance, peel strength, and thermal expansion coefficient.
Figure BDA0003066334200000031
Patent document 12 discloses a thermosetting resin composition containing: a carboxyl group-containing modified ester resin (A); a compound (B) which is at least one selected from the group consisting of an epoxy group-containing compound, an isocyanate group-containing compound, and a blocked isocyanate group-containing compound; and, a heat curing auxiliary (C). Examples of the thermosetting auxiliary (C) include maleimide compounds and citraconimide compounds. The photosensitive resin composition is reported to be excellent in adhesiveness, heat resistance, flexibility, bendability, adhesiveness, electrical insulation, moist heat resistance, and the like, particularly in terms of compatibility between adhesiveness and electrical insulation, and compatibility between bendability and heat resistance.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2004-177668
Patent document 2: japanese patent laid-open publication No. 2004-271838
Patent document 3: japanese patent laid-open publication No. 2005-250434
Patent document 4: international publication No. 2009/072465
Patent document 5: international publication No. 2011/034062
Patent document 6: japanese laid-open patent publication No. 2002-334869
Patent document 7: international publication No. 2004/066377
Patent document 8: japanese patent laid-open publication No. 2007-226170
Patent document 9: japanese patent laid-open No. 2007-226204
Patent document 10: japanese laid-open patent publication No. 2005-141084
Patent document 11: japanese patent laid-open publication No. 2017-071738
Patent document 12: japanese patent laid-open No. 2012 and 131967
Disclosure of Invention
Problems to be solved by the invention
As described above, many film-forming materials for lithography have been proposed. However, there are no materials: in addition to high solvent solubility, which enables application of wet processes such as spin coating and screen printing, the present inventors have also made a compromise between heat resistance, etching resistance, embedding properties into a step substrate, and film flatness at high levels, and have made development of new materials.
Patent document 10 discloses the use of a polymaleimide compound represented by the formula (5a), patent document 11 discloses the use of a bismaleimide compound represented by the formula (1), and patent document 12 discloses the use of a maleimide compound or a citraconimide compound, but the following schemes are not shown in any of the documents: the material is useful for forming a resist underlayer film for lithography, which can be applied to a wet process and is excellent in heat resistance, etching resistance, embedding properties into a step substrate, and film flatness.
The present invention has been made in view of the above problems, and an object thereof is to provide a material for forming a photoresist underlayer film, a composition for forming a photoresist underlayer film containing the material, a photoresist underlayer film using the composition, and a pattern forming method, which are applicable to a wet process and useful for forming a photoresist underlayer film having excellent heat resistance, etching resistance, embedding characteristics into a step substrate, and film flatness.
Means for solving the problems
The present inventors have conducted extensive studies to solve the above problems, and as a result, have found that the above problems can be solved by using a compound having a specific structure, thereby completing the present invention. Namely, the present invention is as follows.
[1]
A film-forming material for lithography, comprising: a compound having a group of formula (0A) and a group of formula (0B).
Figure BDA0003066334200000051
(in the formula (0B),
each R is independently selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 4 carbon atoms. Wherein at least one R is an alkyl group having 1 to 4 carbon atoms. )
[2]
According to [1]The film-forming material for lithography, wherein the compound is represented by the formula (1A)0) And (4) showing.
Figure BDA0003066334200000052
(formula (1A)0) In (1),
each R is independently selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 4 carbon atoms. Wherein at least one R is an alkyl group having 1 to 4 carbon atoms,
z is a 2-valent group having 1 to 100 carbon atoms, which optionally contains a heteroatom. )
[3]
The film forming material for lithography according to [1] or [2], wherein the compound is represented by formula (1A).
Figure BDA0003066334200000061
(in the formula (1A),
each R is independently selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 4 carbon atoms. Wherein at least one R is an alkyl group having 1 to 4 carbon atoms.
Each X is independently selected from the group consisting of a single bond, -O-, -CH2-、-C(CH3)2-、-CO-、-C(CF3)2-, -CONH-and-COO-,
a is selected from the group consisting of a single bond, an oxygen atom, and a divalent group of 1 to 80 carbon atoms optionally containing a hetero atom,
R1each independently a group of carbon number 0 to 30 optionally containing a hetero atom,
m1 is an integer of 0 to 4. )
[4]
According to [3]The film-forming material for lithography described above wherein A is a single bond, an oxygen atom, - (CH)2)p-、-CH2C(CH3)2CH2-、-(C(CH3)2)p-、-(O(CH2)q)p-、-(O(C6H4))p-, or any of the following structures,
Figure BDA0003066334200000062
y is a single bond, -O-, -CH2-、-C(CH3)2-、-C(CF3)2-、
Figure BDA0003066334200000071
p is an integer of 0 to 20,
q is an integer of 0 to 4.
[5]
According to [3]Or [ 4]]The film-forming material for lithography described above, wherein X is each independently a single bond, -O-, -C (CH)3)2-, -CO-, or-COO-,
a is a single bond, an oxygen atom, or the following structure,
Figure BDA0003066334200000072
y is-C (CH)3)2-or-C (CF)3)2-。
[6]
The film forming material for lithography according to [1] or [2], wherein the compound is represented by formula (2A).
Figure BDA0003066334200000073
(in the formula (2A),
r' is independently selected from the group consisting of hydrogen atom and C1-C4 alkyl,
R2each independently a group of carbon number 0 to 10 optionally containing a hetero atom,
m2 is an integer of 0 to 3,
m 2' are each independently an integer of 0 to 4,
n is an integer of 0 to 4,
a plurality of are composed of
Figure BDA0003066334200000081
The group represented comprises at least a group of formula (0A) and a group of formula (0B). )
[7]
The film forming material for lithography according to [1] or [2], wherein the compound is represented by formula (3A).
Figure BDA0003066334200000082
(in the formula (3A),
r' is independently selected from the group consisting of hydrogen atom and C1-C4 alkyl,
R3and R4Each independently a group of carbon number 0 to 10 optionally containing a hetero atom,
m3 is an integer of 0 to 4,
m4 is an integer of 0 to 4,
n is an integer of 1 to 4,
a plurality of are composed of
Figure BDA0003066334200000091
The group represented comprises at least a group of formula (0A) and a group of formula (0B). )
[8]
The film-forming material for lithography according to any one of [2] to [5], wherein the hetero atom is selected from the group consisting of oxygen, fluorine and silicon.
[9]
The material for forming a film for lithography according to any one of [1] to [8], further comprising a crosslinking agent.
[10]
The film forming material for lithography according to [9], wherein the crosslinking agent is at least 1 selected from the group consisting of a phenol compound, an epoxy compound, a cyanate ester compound, an amino compound, a benzoxazine compound, a melamine compound, a guanamine compound, a glycoluril compound, a urea compound, an isocyanate compound and an azide compound.
[11]
The film forming material for lithography according to [9] or [10], wherein the crosslinking agent has at least 1 allyl group.
[12]
The material for forming a film for lithography according to any one of [9] to [11], wherein the content ratio of the crosslinking agent is 0.1 to 100 parts by mass when the mass of the compound is 100 parts by mass.
[13]
The film-forming material for lithography according to any one of [1] to [12], further comprising a crosslinking accelerator.
[14]
The film forming material for lithography according to [13], wherein the crosslinking accelerator contains at least 1 selected from the group consisting of amines, imidazoles, organophosphines, and Lewis acids.
[15]
The material according to [13] or [14], wherein the crosslinking accelerator is contained in an amount of 0.1 to 5 parts by mass based on 100 parts by mass of the compound.
[16]
The film-forming material for lithography according to any one of [1] to [15], further comprising a radical polymerization initiator.
[17]
The material for forming a film for lithography according to [16], wherein the radical polymerization initiator contains at least 1 selected from the group consisting of a ketone-based photopolymerization initiator, an organic peroxide-based polymerization initiator and an azo-based polymerization initiator.
[18]
The material according to [16] or [17], wherein the content of the radical polymerization initiator is 0.05 to 25 parts by mass when the mass of the compound is 100 parts by mass.
[19]
A composition for forming a film for lithography, comprising: [1] the material for forming a film for lithography according to any one of [1] to [18], and a solvent.
[20]
The composition for forming a film for lithography according to [19], further comprising an acid generator.
[21]
The composition for forming a film for lithography according to [19] or [20], which further contains an alkaline compound.
[22]
The composition for forming a film for lithography according to any one of [19] to [21], wherein the film for lithography is an underlayer film for lithography.
[23]
An underlayer film for lithography formed using the composition for forming a film for lithography according to [22 ].
[24]
A method for forming a resist pattern, comprising the steps of:
a step of forming an underlayer film on a substrate using the composition for forming a film for lithography according to [22 ];
forming at least 1 photoresist layer on the underlayer film; and the combination of (a) and (b),
and a step of irradiating a predetermined region of the photoresist layer with radiation and developing the photoresist layer.
[25]
A pattern forming method includes the steps of:
a step of forming an underlayer film on a substrate using the composition for forming a film for lithography according to [22 ];
forming an intermediate layer film on the underlayer film using a resist intermediate layer film material containing silicon atoms;
forming at least 1 photoresist layer on the interlayer film;
a step of forming a resist pattern by irradiating a predetermined region of the photoresist layer with radiation and developing the resist pattern;
etching the intermediate layer film using the resist pattern as a mask;
etching the lower layer film using the obtained intermediate layer film pattern as an etching mask; and the combination of (a) and (b),
and a step of forming a pattern on the substrate by etching the substrate using the obtained lower layer film pattern as an etching mask.
[26]
A purification method comprising the steps of:
a step of dissolving the material for forming a film for lithography according to any one of [1] to [18] in a solvent to obtain an organic phase; and the combination of (a) and (b),
a first extraction step of bringing the organic phase into contact with an acidic aqueous solution to extract impurities in the material for forming a film for lithography,
the solvent used in the aforementioned step of obtaining an organic phase contains a solvent which is not optionally miscible with water.
[27]
The purification method according to [26], wherein the acidic aqueous solution is an aqueous solution of an inorganic acid or an aqueous solution of an organic acid,
the inorganic acid aqueous solution contains 1 or more selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid,
the organic acid aqueous solution contains 1 or more selected from the group consisting of acetic acid, propionic acid, oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid, tartaric acid, citric acid, methanesulfonic acid, phenolsulfonic acid, p-toluenesulfonic acid, and trifluoroacetic acid.
[28]
The purification process according to [26] or [27], wherein the aforementioned solvent which is not optionally miscible with water is 1 or more solvents selected from the group consisting of toluene, 2-heptanone, cyclohexanone, cyclopentanone, methyl isobutyl ketone, propylene glycol monomethyl ether acetate and ethyl acetate.
[29]
The purification method according to any one of [26] to [28], further comprising, after the first extraction step: and a second extraction step of bringing the organic phase into contact with water to extract impurities in the material for forming a film for lithography.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, there can be provided: a material for forming a photoresist underlayer film, a composition for forming a photoresist underlayer film, and a method for forming a photoresist underlayer film using the same, which are applicable to a wet process and are excellent in heat resistance, etching resistance, embedding characteristics into a step substrate, and film flatness.
Detailed Description
Hereinafter, embodiments of the present invention will be described. The following embodiments are illustrative of the present invention, and the present invention is not limited to these embodiments.
[ film Forming Material for lithography ]
One embodiment of the present invention is a material for forming a film for lithography, including: a compound having a group of formula (0A) and a group of formula (0B),
Figure BDA0003066334200000131
(in the formula (0B),
each R is independently selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 4 carbon atoms. Wherein at least one R is an alkyl group having 1 to 4 carbon atoms. ).
The compound having a group of the formula (0A) and a group of the formula (0B) (hereinafter, may be referred to as "citraconic maleimide compound" in the present specification) preferably has 1 or more groups of the formula (0A) and 1 or more groups of the formula (0B). The citraconic maleimide compound can be obtained, for example, by a dehydration ring-closure reaction of a compound having 1 or more primary amino groups in the molecule with maleic anhydride and citraconic anhydride. Examples of the citraconic maleimide compound include polycitraconic maleimide compounds and citraconic maleimide resins.
The material for forming a film for lithography of the present invention may contain at least a compound having a group of the formula (0A) and a group of the formula (0B), and may contain another compound having a group of the formula (0A) and/or a compound having a group of the formula (0B).
Examples of the compound having a group of the formula (0A) include compounds having 2 groups of the formula (0A) in the molecule, and examples of the compound having a group of the formula (0B) include compounds having 2 groups of the formula (0B) in the molecule.
The content of the citraconic maleimide compound in the film-forming material for lithography according to the present embodiment is preferably 51 to 100 mass%, more preferably 60 to 100 mass%, even more preferably 70 to 100 mass%, and even more preferably 80 to 100 mass%, from the viewpoint of heat resistance and etching resistance.
In order to improve the heat resistance of the conventional underlayer film forming composition, the citraconic maleimide compound in the film forming material for lithography according to the present embodiment may be used as an additive. The content of the citraconic maleimide compound in this case is preferably 1 to 50% by mass, more preferably 1 to 30% by mass.
The citraconic maleimide compound in the material for forming a film for lithography according to the present embodiment is characterized by having a function other than the function as an acid generator or a basic compound for forming a film for lithography.
The molecular weight of the citraconic maleimide compound in the present embodiment is preferably 450 or more. Since the molecular weight is 450 or more, generation of sublimates or decomposed products can be suppressed even by high-temperature baking in forming a thin film. The molecular weight is more preferably 500 or more, still more preferably 550 or more, and still more preferably 600 or more. The upper limit of the molecular weight is not particularly limited, and may be, for example, 2000, 1750, 1500, 1250, 1000, or the like.
The citraconic maleimide compound in the present embodiment is more preferably represented by the following formula (1A)0) The compound shown in the specification.
Figure BDA0003066334200000141
(formula (1A)0) In (1),
each R is independently selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 4 carbon atoms. Wherein at least one R is an alkyl group having 1 to 4 carbon atoms.
Z is a C1-100 divalent hydrocarbon group optionally containing a heteroatom. )
The material for forming a film for lithography of the present invention may contain, as described above, other compounds having a group of formula (0A) and/or compounds having a group of formula (0B) in addition to the citraconic maleimide compound.
Examples of the compound having a group of the formula (0A) and the compound having a group of the formula (0B) include bismaleimides and biscitraconimides represented by the following structures, respectively.
Figure BDA0003066334200000151
(in the above structure, Z is represented by the formula (1A)0) Wherein Z has the same meaning and corresponds to a 2-valent hydrocarbon moiety of 1 to 100 carbon atoms optionally containing a heteroatom in the formula (1A) described later. )
The number of carbon atoms of the hydrocarbon group may be 1 to 80, 1 to 60, 1 to 40, 1 to 20, etc. Examples of the hetero atom include oxygen, nitrogen, sulfur, fluorine, and silicon, and among them, oxygen, fluorine, and silicon are preferable.
The citraconic maleimide compound in the present embodiment is more preferably a compound represented by the following formula (1A).
Figure BDA0003066334200000152
In the formula (1A), the compound (A),
each R is independently selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 4 carbon atoms. Wherein at least one R is an alkyl group having 1 to 4 carbon atoms.
Each X is independently selected from the group consisting of a single bond, -O-, -CH2-、-C(CH3)2-、-CO-、-C(CF3)2-, -CONH-and-COO-,
a is selected from the group consisting of a single bond, an oxygen atom, and a C1-80 divalent hydrocarbon group optionally containing a heteroatom (e.g., oxygen, nitrogen, sulfur, fluorine),
R1each independently being optionally containing heteroatoms (e.g. oxygen, nitrogen, or nitrogen,Sulfur, fluorine, chlorine, bromine, iodine) having 0 to 30 carbon atoms,
m1 is an integer of 0 to 4.
From the viewpoint of improving heat resistance, in the formula (1A), a is more preferably a single bond, an oxygen atom, - (CH)2)p-、-CH2C(CH3)2CH2-、-(C(CH3)2)p-、-(O(CH2)q)p-、-(O(C6H4))p-, or any of the following structures,
Figure BDA0003066334200000161
y is a single bond, -O-, -CH2-、-C(CH3)2-、-C(CF3)2-、
Figure BDA0003066334200000162
p is an integer of 0 to 20,
q is an integer of 0 to 4.
In the formula (1A), more preferred is
X is each independently a single bond, -O-, -C (CH)3)2-, -CO-, or-COO-,
a is a single bond, an oxygen atom, or the following structure,
Figure BDA0003066334200000163
y is-C (CH)3)2-or-C (CF)3)2-。
From the viewpoint of heat resistance, X is preferably a single bond, and from the viewpoint of solubility, -COO-is preferred.
From the viewpoint of improving heat resistance, Y is preferably a single bond.
R1Preferably optionally containing heteroatoms (e.g. oxygen, nitrogen, sulphur, fluorine,Chlorine, bromine, iodine) of 0 to 20 or 0 to 10 carbon atoms. From the viewpoint of improving solubility in organic solvents, R1Hydrocarbyl groups are preferred. For example as R1Examples thereof include alkyl groups (for example, alkyl groups having 1 to 6 or 1 to 3 carbon atoms), and specific examples thereof include methyl groups and ethyl groups.
m1 is preferably an integer of 0 to 2, more preferably 1 or 2 from the viewpoint of availability of raw materials and improvement of solubility.
From the viewpoint of improving heat resistance, the citraconic maleimide compound in the present embodiment is preferably a compound represented by the following formula (2A) or the following formula (3A). In addition, the compound represented by the following formula (2A) or the following formula (3A) more preferably has at least 1 group of the following formula (0B'):
Figure BDA0003066334200000171
in the above-mentioned formula (2),
r' is independently selected from the group consisting of hydrogen atom and C1-C4 alkyl,
R2each independently is a group of carbon number 0-10 optionally containing heteroatoms (e.g., oxygen, nitrogen, sulfur, fluorine, chlorine, bromine, iodine). In addition, from the viewpoint of improving solubility in organic solvents, R2Hydrocarbyl groups are preferred. For example, as R2Examples thereof include alkyl groups (for example, alkyl groups having 1 to 6 or 1 to 3 carbon atoms), and specific examples thereof include methyl groups and ethyl groups.
m2 is an integer of 0 to 3. M2 is preferably 0 or 1, and more preferably 0 from the viewpoint of availability of raw materials.
m 2' are each independently an integer of 0 to 4. M 2' is preferably 0 or 1, and more preferably 0 from the viewpoint of availability of raw materials.
n is an integer of 0 to 4. N is preferably an integer of 1 to 4, and more preferably an integer of 1 to 3 from the viewpoint of improving heat resistance.
When n is 1 or more, monomers that may cause sublimates can be removed, and both flatness and heat resistance can be expected, and n is more preferably 1.
A plurality of are composed of
Figure BDA0003066334200000181
The group represented comprises at least a group of formula (0A) and a group of formula (0B).
Figure BDA0003066334200000182
In the above-mentioned formula (3A),
r' is independently selected from the group consisting of hydrogen atom and C1-C4 alkyl,
R3and R4Each independently is a group of carbon number 0-10 optionally containing heteroatoms (e.g., oxygen, nitrogen, sulfur, fluorine, chlorine, bromine, iodine). In addition, from the viewpoint of improving solubility in organic solvents, R3And R4Hydrocarbyl groups are preferred. For example, as R3And R4Examples thereof include alkyl groups (for example, alkyl groups having 1 to 6 or 1 to 3 carbon atoms), and specific examples thereof include methyl groups and ethyl groups.
m3 is an integer of 0 to 4. M3 is preferably an integer of 0 to 2, and more preferably 0 from the viewpoint of availability of raw materials.
m4 is an integer of 0 to 4. M4 is preferably an integer of 0 to 2, and more preferably 0 from the viewpoint of availability of raw materials.
n is an integer of 1 to 4. In addition, n is preferably an integer of 1 to 2 from the viewpoint of availability of raw materials. From the viewpoint of improving heat resistance, n is more preferably an integer of 2 to 4.
When n is 2 or more, monomers that may cause sublimation can be removed, and a balance between flatness and heat resistance can be expected, and n is more preferably 2.
The material for forming a film for lithography according to this embodiment can be applied to a wet process. The material for forming a film for lithography according to the present embodiment has an aromatic structure and has a maleimide skeleton and a citraconimide skeleton, which are rigid, and even when baked at a high temperature, the maleimide skeleton and the citraconimide skeleton cause a crosslinking reaction to exhibit high heat resistance. As a result, deterioration of the film during high-temperature baking is suppressed, and an underlayer film having excellent etching resistance to oxygen plasma etching and the like can be formed. Further, the material for forming a film for lithography according to the present embodiment has a high solubility in an organic solvent and a high solubility in a safe solvent, although it has an aromatic structure. Further, the lower layer film for lithography formed from the composition for forming a film for lithography of the present embodiment described later is excellent not only in embedding property into a step substrate and flatness of the film, and stability of product quality, but also in adhesion to a resist layer and a material of a resist intermediate layer film, and therefore an excellent resist pattern can be obtained.
Specific examples of the citraconic maleimide compound used in the present embodiment include: citraconic maleimide obtained from diamine containing phenylene skeleton, such as m-phenylenediamine, 4-methyl-1, 3-phenylenediamine, 4-diaminodiphenylmethane, 4-diaminodiphenylsulfone, 1, 3-bis (3-aminophenoxy) benzene, 1, 3-bis (4-aminophenoxy) benzene, 1, 4-bis (3-aminophenoxy) benzene, 1, 4-bis (4-aminophenoxy) benzene, etc.;
prepared from bis (3-ethyl-5-methyl-4-aminophenyl) methane, 1-bis (3-ethyl-5-methyl-4-aminophenyl) ethane, 2-bis (3-ethyl-5-methyl-4-aminophenyl) propane, N '-4, 4' -diamino-3, 3 '-dimethyl-diphenylmethane, N' -4,4 '-diamino-3, 3' -dimethyl-1, 1-diphenylethane, N '-4, 4' -diamino-3, 3 '-dimethyl-1, 1-diphenylpropane, N' -4,4 '-diamino-3, 3' -diethyl-diphenylmethane, Citraconic maleimide obtained from diamine containing diphenylalkane skeleton such as N, N '-4, 4' -diamino 3,3 '-di-N-propyl-diphenylmethane and N, N' -4,4 '-diamino 3, 3' -di-N-butyl-diphenylmethane;
citraconic maleimide obtained from diamine containing biphenyl skeleton, such as N, N '-4, 4' -diamino-3, 3 '-dimethyl-acenaphthene, N' -4,4 '-diamino-3, 3' -diethyl-acenaphthene, etc.;
citraconic maleimide obtained from diamine with aliphatic skeleton such as 1, 6-hexanediamine, 1, 6-diamino (2,2, 4-trimethyl) hexane, 1, 3-dimethylene cyclohexane diamine, and 1, 4-dimethylene cyclohexane diamine;
prepared from 1, 3-bis (3-aminopropyl) -1,1,2, 2-tetramethyldisiloxane, 1, 3-bis (3-aminobutyl) -1,1,2, 2-tetramethyldisiloxane, bis (4-aminophenoxy) dimethylsilane, 1, 3-bis (4-aminophenoxy) tetramethyldisiloxane, 1,3, 3-tetramethyl-1, 3-bis (4-aminophenyl) disiloxane, 1,3, 3-tetraphenoxy-1, 3-bis (2-aminoethyl) disiloxane, 1,3, 3-tetraphenyl-1, 3-bis (3-aminopropyl) disiloxane, 1,1,3, 3-tetramethyl-1, 3-bis (2-aminoethyl) disiloxane, 1,3, 3-tetramethyl-1, 3-bis (3-aminopropyl) disiloxane, 1,3, 3-tetramethyl-1, 3-bis (4-aminobutyl) disiloxane, 1, 3-dimethyl-1, 3-dimethoxy-1, 3-bis (4-aminobutyl) disiloxane, 1,3,3,5, 5-hexamethyl-1, 5-bis (4-aminophenyl) trisiloxane, 1,5, 5-tetraphenyl-3, 3-dimethyl-1, 5-bis (3-aminopropyl) trisiloxane, 1,5, 5-tetraphenyl-3, 3-dimethoxy-1, 5-bis (4-aminobutyl) trisiloxane, 1,5, 5-tetraphenyl-3, 3-dimethoxy-1, 5-bis (5-aminopentyl) trisiloxane, 1,5, 5-tetramethyl-3, 3-dimethoxy-1, 5-bis (2-aminoethyl) trisiloxane, 1,5, 5-tetramethyl-3, 3-dimethoxy-1, 5-bis (4-aminobutyl) trisiloxane, 1,5, 5-tetramethyl-3, 3-dimethoxy-1, 5-bis (5-aminopentyl) trisiloxane, 1,3, citraconic maleimide obtained from a diaminosiloxane such as 3,5, 5-hexamethyl-1, 5-bis (3-aminopropyl) trisiloxane, 1,3,3,5, 5-hexaethyl-1, 5-bis (3-aminopropyl) trisiloxane, 1,3,3,5, 5-hexapropyl-1, 5-bis (3-aminopropyl) trisiloxane and the like; and the like.
Among the citraconic maleimide compounds, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, N '-4, 4' - [3,3 '-dimethyl-diphenylmethane ] citraconic imide maleimide, and N, N' -4,4 '- [3, 3' -diethyl-diphenylmethane ] citraconic imide maleimide are particularly preferable because they are excellent in curability and heat resistance.
Among the above biscitraconimide compounds, bis (3-ethyl-5-methyl-4-citraconimidophenyl) methane, N '-4, 4' - [3,3 '-dimethyl-diphenylmethane ] citraconimidomaleimide and N, N' -4,4 '- [3, 3' -diethyl-diphenylmethane ] citraconimidomaleimide are particularly preferable because they are excellent in solvent solubility.
< crosslinking agent >
The material for forming a film for lithography of the present embodiment may further contain a crosslinking agent as needed from the viewpoint of suppressing a decrease in curing temperature, intermixing (intermixing), and the like in addition to the compound having the group of formula (0A) and the group of formula (0B).
The crosslinking agent is not particularly limited as long as it is capable of crosslinking with a maleimide group and a citraconimide group, and any known crosslinking system can be used. The crosslinking agent that can be used in the present embodiment is not particularly limited, and examples thereof include phenol compounds, epoxy compounds, cyanate ester compounds, amino compounds, benzoxazine compounds, acrylate compounds, melamine compounds, guanamine compounds, glycoluril compounds, urea compounds, isocyanate compounds, azide compounds, and the like. These crosslinking agents may be used alone in 1 kind or in combination of 2 or more kinds. Among these, a benzoxazine compound, an epoxy compound, or a cyanate ester compound is preferable, and a benzoxazine compound is more preferable from the viewpoint of improving etching resistance.
In the crosslinking reaction between the maleimide group and the citraconimide group and the crosslinking agent, for example, an active group (phenolic hydroxyl group, epoxy group, cyanate group, amino group, or phenolic hydroxyl group formed by ring-opening of an alicyclic portion of benzoxazine) of these crosslinking agents is crosslinked by addition reaction with a carbon-carbon double bond constituting the maleimide group and the citraconimide group, and further, 2 carbon-carbon double bonds of the compound in the present embodiment are polymerized and crosslinked.
As the phenol compound, a known compound can be used. Examples thereof include those described in International publication No. 2018-016614. Preferably, an aralkyl type phenol resin is preferable from the viewpoint of heat resistance and solubility.
The epoxy compound may be a known compound selected from those having 2 or more epoxy groups in 1 molecule. Examples thereof include those described in International publication No. 2018-016614. The epoxy resins may be used alone or in combination of 2 or more. Epoxy resins that are solid at ordinary temperatures, such as epoxy resins obtained from phenol aralkyl resins and biphenyl aralkyl resins, are preferred from the viewpoint of heat resistance and solubility.
The cyanate ester compound is not particularly limited as long as it has 2 or more cyanate groups in 1 molecule, and a known cyanate ester compound can be used. For example, those described in international publication 2011-108524 are included, and in the present embodiment, a preferable cyanate ester compound is a compound having a structure in which a hydroxyl group of a compound having 2 or more hydroxyl groups in 1 molecule is substituted with a cyanate ester group. The cyanate ester compound preferably has an aromatic group, and a compound having a structure in which a cyanate group is directly bonded to an aromatic group can be suitably used. Examples of such cyanate ester compounds include those described in international publication No. 2018-016614. The cyanate ester compound may be used alone or in a suitable combination of 2 or more. The cyanate ester compound may be in any form of a monomer, an oligomer, and a resin.
Examples of the amino compound include those described in International publication No. 2018-016614.
The structure of the oxazine of the benzoxazine compound is not particularly limited, and examples thereof include the structures of oxazines having aromatic groups including condensed polycyclic aromatic groups, such as benzoxazine and naphthoxazine.
Examples of the benzoxazine compound include compounds represented by the following general formulae (a) to (f). In the following general formula, the bond shown toward the center of the ring represents any carbon constituting the ring and bonded to a substitutable group.
Figure BDA0003066334200000221
In the general formulae (a) to (c), R1And R2Independently represents an organic group having 1 to 30 carbon atoms. In the general formulae (a) to (f), R3To R6Independently represents hydrogen or a hydrocarbon group having 1 to 6 carbon atoms. In the general formulae (c), (d) and (f), X independently represents a single bond, -O-, -S-, -SO2-、-CO-、-CONH-、-NHCO-、-C(CH3)2-、-C(CF3)2-、-(CH2)m-、-O-(CH2)m-O-、-S-(CH2) m-S-. Where m is an integer of 1 to 6. In the general formulae (e) and (f), Y independently represents a single bond, -O-, -S-, -CO-, -C (CH)3)2-、-C(CF3)2Or an alkylene group having 1 to 3 carbon atoms.
The benzoxazine compound includes oligomers and polymers having an oxazine structure in a side chain, and oligomers and polymers having a benzoxazine structure in a main chain.
The benzoxazine compound can be produced by the same method as that described in the pamphlet of International publication No. 2004/009708, Japanese patent application laid-open Nos. 11-12258 and 2004-352670.
Examples of the melamine compound include those described in International publication No. 2018-016614.
Examples of the guanamine compound include those described in International publication No. 2018-016614.
Examples of the glycoluril compound include those described in International publication No. 2018-016614.
Examples of the urea compound include those described in International publication No. 2018-016614.
In the present embodiment, a crosslinking agent having at least 1 allyl group can be used from the viewpoint of improving the crosslinkability. Examples of the crosslinking agent having at least 1 allyl group include those described in International publication No. 2018-016614. The crosslinking agent having at least 1 allyl group may be used alone or in combination of 2 or more. From the viewpoint of excellent compatibility with the compound 0A and the compound 0B, allylphenols such as 2, 2-bis (3-allyl-4-hydroxyphenyl) propane, 1,1,1,3,3, 3-hexafluoro-2, 2-bis (3-allyl-4-hydroxyphenyl) propane, bis (3-allyl-4-hydroxyphenyl) sulfone, bis (3-allyl-4-hydroxyphenyl) sulfide, and bis (3-allyl-4-hydroxyphenyl) ether are preferable.
The material for forming a film for lithography according to the present embodiment may be compounded with the above-mentioned crosslinking agent alone or after compounding, and crosslinked and cured by a known method to form a film for lithography according to the present embodiment. Examples of the crosslinking method include thermal curing, photo curing and the like.
The content ratio of the crosslinking agent is usually in the range of 0.1 to 10000 parts by mass when the mass of the citraconic maleimide compound is 100 parts by mass, and from the viewpoint of heat resistance and solubility, the content ratio is preferably in the range of 0.1 to 1000 parts by mass, more preferably in the range of 0.1 to 100 parts by mass, still more preferably in the range of 1 to 50 parts by mass, and still more preferably in the range of 1 to 30 parts by mass.
The material for forming a film for lithography according to the present embodiment may use a crosslinking accelerator for accelerating a crosslinking reaction or a curing reaction, if necessary.
The crosslinking accelerator is not particularly limited as long as it accelerates crosslinking and curing reactions, and examples thereof include amines, imidazoles, organophosphines, and lewis acids. These crosslinking accelerators may be used alone in 1 kind or in combination of 2 or more kinds. Of these, imidazoles and organophosphines are preferred, and imidazoles are more preferred from the viewpoint of lowering the crosslinking temperature.
Examples of the crosslinking accelerator include those described in International publication No. 2018-016614.
The amount of the crosslinking accelerator to be blended is preferably 0.01 to 10 parts by mass, more preferably 0.01 to 5 parts by mass, and still more preferably 0.01 to 3 parts by mass, from the viewpoint of ease of control and economy, when the mass of the compound having the group of formula (0A) and the group of formula (0B) is 100 parts by mass.
The material for forming a film for lithography according to the present embodiment may use a latent alkali generator for promoting a crosslinking reaction or a curing reaction, if necessary. The latent alkali-producing agent is a curing accelerator which exhibits no activity under ordinary storage conditions but exhibits activity in response to an external stimulus (e.g., heat, light, etc.). As the alkali-producing agent, those which generate alkali by thermal decomposition, those which generate alkali by light irradiation (photoalkali-producing agents), and the like are known and can be used.
Photobase generators are neutral compounds that generate a base upon exposure to electromagnetic waves. Examples of the amine-producing substance include benzyl carbamates, benzoin carbamates, 0-carbamoylhydroxylamines, O-carbamoyloximes, and RR '-N-CO-OR "(here, R, R' is each independently hydrogen OR a lower alkyl group, and R" is nitrobenzyl OR. alpha. methyl nitrobenzyl). In order to ensure storage stability when added to a solution and suppress volatilization at baking from a low vapor pressure, a borate compound that generates a tertiary amine or a quaternary ammonium salt containing a dithiocarbamate as an anion (c.e. hoyle, et. al., Macromolucules, 32,2793(1999)) and the like are particularly preferable.
Specific examples of the latent alkali-producing agent include the following, but the present invention is not limited to these.
(examples of ruthenium (III) hexammine Triphenylalkyl Borate)
Ruthenium (III) hexamine tris (triphenylmethyl borate), ruthenium (III) hexamine tris (triphenylethyl borate), ruthenium (III) hexamine tris (triphenylpropyl borate), ruthenium (III) hexamine tris (triphenylbutyl borate), ruthenium (III) hexamine tris (triphenylhexyl borate), ruthenium (III) hexamine tris (triphenyloctyl borate), ruthenium (III) hexamine tris (triphenyloctadecyl borate), ruthenium (III) hexamine tris (triphenylisopropyl borate), ruthenium (III) hexamine tris (triphenylisobutyl borate), ruthenium (III) hexamine tris (triphenyl-sec-butyl borate), ruthenium (III) hexamine tris (triphenyl-tert-butyl borate), ruthenium (III) hexamine tris (triphenylneopentyl borate), and the like.
(examples of ruthenium (III) hexammine triphenylborate)
Hexaammineruthenium (III) tris (triphenylcyclopentyl borate), hexaammineruthenium (III) tris (triphenylcyclohexyl borate), hexaammineruthenium (III) tris [ triphenyl (4-decylcyclohexyl) borate ], hexaammineruthenium (III) tris [ triphenyl (fluoromethyl) borate ], hexaammineruthenium (III) tris [ triphenyl (chloromethyl) borate ], hexaammineruthenium (III) tris [ triphenyl (bromomethyl) borate ], hexaammineruthenium (III) tris [ triphenyl (trifluoromethyl) borate ], hexaammineruthenium (III) tris [ triphenyl (trichloromethyl) borate ], hexaammineruthenium (III) tris [ triphenyl (hydroxymethyl) borate ], hexaammineruthenium (III) tris [ triphenyl (carboxymethyl) borate ], hexaammineruthenium (III) tris [ triphenyl (cyanomethyl) borate ], hexaammineruthenium (III) tris [ triphenyl (nitromethyl) borate ], (III) hexaammineruthenium (III) tris [ triphenyl (nitromethyl) borate ], (III), Ruthenium (III) hexammoniate tris [ triphenyl (azidomethyl) borate ], and the like.
(example of ruthenium (III) hexammine triarylbutyl Borate)
Hexaammineruthenium (III) tris [ tris (1-naphthyl) butyl borate ], hexaammineruthenium (III) tris [ tris (2-naphthyl) butyl borate ], hexaammineruthenium (III) tris [ tris (o-tolyl) butyl borate ], hexaammineruthenium (III) tris [ tris (m-tolyl) butyl borate ], hexaammineruthenium (III) tris [ tris (p-tolyl) butyl borate ], hexaammineruthenium (III) tris [ tris (2, 3-xylyl) butyl borate ], hexaammineruthenium (III) tris [ tris (2, 5-xylyl) butyl borate ], and the like.
(example of ruthenium (III) tris (triphenylbutylborate))
Tris (ethylenediamine) ruthenium (III) tris (triphenylbutylborate), cis-diaminebis (ethylenediamine) ruthenium (III) tris (triphenylbutylborate), trans-diaminebis (ethylenediamine) ruthenium (III) tris (triphenylbutylborate), tris (trimethylenediamine) ruthenium (III) tris (triphenylbutylborate), tris (propylenediamine) ruthenium (III) tris (triphenylbutylborate), tetraammine { (-) - (propylenediamine) } ruthenium (III) tris (triphenylbutylborate), tris (trans-1, 2-cyclohexanediamine) ruthenium (III) tris (triphenylbutylborate), bis (diethylenetriamine) ruthenium (III) tris (triphenylbutylborate), bis (pyridine) bis (ethylenediamine) ruthenium (III) tris (triphenylbutylborate), bis (imidazole) bis (ethylenediamine) ruthenium (III) tris (triphenylbutylborate), and the like.
The above-mentioned latent alkali-producing agent can be easily produced by mixing a halogen salt, sulfate, nitrate, acetate or the like of each complex ion with an alkali metal borate in an appropriate solvent such as water, alcohol or an aqueous organic solvent. Halogen salts, sulfates, nitrates, acetates, etc. of each complex ion to be used as these raw materials are easily available as commercial products, and their synthesis methods are described in, for example, the editions of the chemical society of japan, the new experimental chemistry lecture 8 (synthesis III of inorganic compounds), the pill good (1977), etc.
The content of the latent alkali-producing agent may be a stoichiometrically required amount with respect to the mass of the maleimide compound, and is preferably 0.01 to 25 parts by mass, more preferably 0.01 to 10 parts by mass, when the mass of the maleimide compound is 100 parts by mass. When the content of the latent alkali-producing agent is 0.01 parts by mass or more, curing of the maleimide compound tends to be prevented from becoming insufficient, while when the content of the latent alkali-producing initiator is 25 parts by mass or less, long-term storage stability of the material for forming a film for lithography at room temperature tends to be prevented from being impaired.
< free radical polymerization initiator >
The material for forming a film for lithography according to the present embodiment may contain a radical polymerization initiator as needed. The radical polymerization initiator may be a photopolymerization initiator that initiates radical polymerization by light, or a thermal polymerization initiator that initiates radical polymerization by heat.
Examples of such radical polymerization initiators include those described in International publication No. 2018-016614. Examples of the radical polymerization initiator include a ketone-based photopolymerization initiator, an organic peroxide-based polymerization initiator, and an azo-based polymerization initiator. The radical polymerization initiator in the present embodiment may be used alone in 1 kind, or may be used in combination with 2 or more kinds.
The content of the radical polymerization initiator may be a stoichiometrically required amount with respect to the mass of the citraconic maleimide compound, and is preferably 0.05 to 25 parts by mass, more preferably 0.1 to 10 parts by mass, when the mass of the maleimide compound is 100 parts by mass. When the content of the radical polymerization initiator is 0.05 parts by mass or more, curing of the maleimide compound tends to be prevented from becoming insufficient, while when the content of the radical polymerization initiator is 25 parts by mass or less, long-term storage stability of the material for forming a film for lithography at room temperature tends to be prevented from being impaired.
[ method of purifying Material for Forming film for lithography ]
The material for forming a film for lithography according to the present embodiment can be cleaned and purified with an acidic aqueous solution. The purification method comprises the following steps: the method for producing a metal-containing organic phase for lithography includes dissolving a material for forming a film for lithography in an organic solvent which is not miscible with water to obtain an organic phase, bringing the organic phase into contact with an acidic aqueous solution, and performing an extraction treatment (first extraction step) to move a metal component contained in the organic phase containing the material for forming a film for lithography and the organic solvent to an aqueous phase, and then separating the organic phase from the aqueous phase. By this purification, the contents of various metals in the material for forming a film for lithography according to the present embodiment can be significantly reduced.
The organic solvent which is not miscible with water is not particularly limited, and is preferably an organic solvent which can be safely used in a semiconductor production process. The amount of the organic solvent used is usually about 1 to 100 times by mass based on the compound used.
Specific examples of the organic solvent to be used include those described in International publication No. 2015/080240. Among them, toluene, 2-heptanone, cyclohexanone, cyclopentanone, methyl isobutyl ketone, propylene glycol monomethyl ether acetate, ethyl acetate and the like are preferable, and cyclohexanone and propylene glycol monomethyl ether acetate are more preferable. These organic solvents may be used alone, or 2 or more kinds may be used in combination.
The acidic aqueous solution can be suitably selected from aqueous solutions obtained by dissolving generally known organic and inorganic compounds in water, and examples thereof include those described in international publication 2015/080240. These acidic aqueous solutions may be used alone, or 2 or more kinds may be used in combination. Examples of the acidic aqueous solution include an aqueous solution of an inorganic acid and an aqueous solution of an organic acid. Examples of the aqueous solution of an inorganic acid include aqueous solutions containing 1 or more kinds selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid. Examples of the aqueous organic acid solution include aqueous solutions containing 1 or more selected from the group consisting of acetic acid, propionic acid, oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid, tartaric acid, citric acid, methanesulfonic acid, phenolsulfonic acid, p-toluenesulfonic acid, and trifluoroacetic acid. The acidic aqueous solution is preferably an aqueous solution of sulfuric acid, nitric acid, and a carboxylic acid such as acetic acid, oxalic acid, tartaric acid, or citric acid, more preferably an aqueous solution of sulfuric acid, oxalic acid, tartaric acid, or citric acid, and still more preferably an aqueous solution of oxalic acid. Polycarboxylic acids such as oxalic acid, tartaric acid, and citric acid are thought to be able to further remove metals because they coordinate metal ions and produce a chelating effect. In addition, water used here is preferably one having a small metal content, for example, ion-exchanged water or the like, in accordance with the object of the present invention.
The pH of the acidic aqueous solution is not particularly limited, and if the acidity of the aqueous solution is excessively increased, the compound or resin used is adversely affected, and therefore, the pH is usually about 0 to 5, and more preferably about 0 to 3.
The amount of the acidic aqueous solution to be used is not particularly limited, but if the amount is too small, the number of extraction steps for removing metals is required to be increased, whereas if the amount is too large, the total amount of the aqueous solution may be increased, which may cause problems in handling. The amount of the aqueous solution is usually 10 to 200 parts by mass, preferably 20 to 100 parts by mass, based on the solution of the material for forming a film for lithography.
The metal component can be extracted by contacting the aforementioned acidic aqueous solution with a solution (B) containing the film-forming material for lithography and an organic solvent which is not optionally miscible with water.
The temperature for the extraction is usually 20 to 90 ℃, preferably 30 to 80 ℃. The extraction operation is performed by, for example, sufficiently mixing the components by stirring and then leaving the mixture to stand. Thereby, the metal component contained in the solution containing the compound and the organic solvent used moves to the aqueous phase. In addition, the acidity of the solution is reduced by this operation, and the deterioration of the compound to be used can be suppressed.
After the extraction treatment, the mixture is separated into a solution phase containing the compound and the organic solvent to be used and an aqueous phase, and the solution containing the organic solvent is recovered by decantation or the like. The time for the standing is not particularly limited, but if the time for the standing is too short, the separation of the aqueous phase from the solution phase containing the organic solvent is poor, which is not preferable. The time for standing is usually 1 minute or more, more preferably 10 minutes or more, and still more preferably 30 minutes or more. The extraction treatment may be performed only 1 time, but it is also effective to repeat the operations of mixing, standing, and separating a plurality of times.
When such an extraction treatment is performed using an acidic aqueous solution, it is preferable that after the treatment, the organic phase containing the organic solvent extracted and recovered from the aqueous solution is further subjected to an extraction treatment with water (second extraction step). The extraction operation is performed by sufficiently mixing them with stirring and then standing. The resulting solution is then separated into a solution phase containing the compound and the organic solvent, and an aqueous phase, and the solution phase is thus recovered by decantation or the like. In addition, water used here is preferably one having a small metal content, for example, ion-exchanged water or the like, in accordance with the object of the present invention. The extraction treatment can be carried out only 1 time, but it is also effective to repeat the operations of mixing, standing, and separating a plurality of times. Conditions such as the ratio of both used, temperature, and time in the extraction treatment are not particularly limited, and the same can be applied as in the case of the contact treatment with an acidic aqueous solution.
The water mixed in the solution containing the film-forming material for lithography and the organic solvent thus obtained can be easily removed by performing an operation such as distillation under reduced pressure. In addition, the concentration of the compound can be adjusted to any concentration by adding an organic solvent as needed.
The method of obtaining only the film-forming material for lithography from the obtained solution containing the organic solvent may be carried out by a known method such as removal under reduced pressure, separation by reprecipitation, or a combination thereof. If necessary, known treatments such as concentration, filtration, centrifugation, and drying may be performed.
[ composition for Forming film for lithography ]
The composition for forming a film for lithography according to the present embodiment contains the above-described material for forming a film for lithography and a solvent. The film for lithography is, for example, a lower layer film for lithography.
The composition for forming a film for lithography according to the present embodiment can be applied to a substrate, and then heated as necessary to evaporate a solvent, and then heated or irradiated with light to form a desired cured film. The coating method of the composition for forming a film for lithography according to the present embodiment is arbitrary, and for example, a spin coating method, a dipping method, a flow coating method, an ink jet method, a spray method, a bar coating method, a gravure coating method, a slit coating method, a roll coating method, a transfer printing method, a brush coating method, a blade coating method, an air knife coating method, or the like can be suitably used.
The heating temperature of the film is not particularly limited for the purpose of evaporating the solvent, and may be, for example, 40 to 400 ℃. The heating method is not particularly limited, and for example, evaporation can be performed in a suitable atmosphere such as the atmosphere, an inert gas such as nitrogen, or a vacuum using a hot plate or an oven. The heating temperature and the heating time may be selected to be suitable for the process of the target electronic device, and heating conditions may be selected so that the physical property values of the obtained film are suitable for the required characteristics of the electronic device. The conditions for the light irradiation are not particularly limited, and the irradiation energy and the irradiation time may be appropriately selected depending on the material for forming the film for lithography used.
< solvent >
The solvent used in the composition for forming a film for lithography according to the present embodiment is not particularly limited as long as the citraconic maleimide compound is at least dissolved, and a known solvent can be suitably used.
Specific examples of the solvent include those described in international publication 2013/024779. These solvents may be used alone in 1 kind or in combination of 2 or more kinds.
Among the above solvents, cyclohexanone, propylene glycol monomethyl ether acetate, ethyl lactate, methyl hydroxyisobutyrate, and anisole are particularly preferable from the viewpoint of safety.
The content of the solvent is not particularly limited, and is preferably 25 to 9900 parts by mass, more preferably 400 to 7900 parts by mass, and still more preferably 900 to 4900 parts by mass, when the mass of the maleimide compound in the material for forming a film for lithography is 100 parts by mass, from the viewpoint of solubility and film formation.
< acid generating agent >
The composition for forming a film for lithography according to the present embodiment may contain an acid generator as needed from the viewpoint of further promoting the crosslinking reaction and the like. As the acid generator, a substance that generates an acid by thermal decomposition, a substance that generates an acid by light irradiation, and the like are known and can be used.
Examples of the acid generator include those described in international publication No. 2013/024779. Among these, onium salts such as triphenylsulfonium trifluoromethanesulfonate, (p-tert-butoxyphenyl) diphenylsulfonium trifluoromethanesulfonate, tris (p-tert-butoxyphenyl) sulfonium trifluoromethanesulfonate, triphenylsulfonium p-toluenesulfonate, bis (p-tert-butoxyphenyl) diphenylsulfonium p-toluenesulfonate, tris (p-tert-butoxyphenyl) sulfonium p-toluenesulfonate, trinaphthylsulfonium trifluoromethanesulfonate, cyclohexylmethyl (2-oxocyclohexyl) sulfonium trifluoromethanesulfonate, (2-norbornyl) methyl (2-oxocyclohexyl) sulfonium trifluoromethanesulfonate and 1, 2' -naphthylcarbonylmethyltetrahydrothiophenium trifluoromethanesulfonate are particularly preferably used; diazomethane derivatives such as bis (phenylsulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (n-butylsulfonyl) diazomethane, bis (isobutylsulfonyl) diazomethane, bis (sec-butylsulfonyl) diazomethane, bis (n-propylsulfonyl) diazomethane, bis (isopropylsulfonyl) diazomethane, and bis (tert-butylsulfonyl) diazomethane; glyoxime derivatives such as bis- (p-toluenesulfonyl) - α -dimethylglyoxime and bis- (n-butanesulfonyl) - α -dimethylglyoxime, and disulfone derivatives such as bis-naphthylsulfonylmethane; and sulfonate derivatives of N-hydroxyimide compounds such as N-hydroxysuccinimide methanesulfonate, N-hydroxysuccinimide trifluoromethanesulfonate, N-hydroxysuccinimide 1-propane sulfonate, N-hydroxysuccinimide 2-propane sulfonate, N-hydroxysuccinimide 1-pentane sulfonate, N-hydroxysuccinimide p-toluene sulfonate, N-hydroxynaphthalimide methanesulfonate, and N-hydroxynaphthalimide benzenesulfonate.
The content of the acid generator in the composition for forming a film for lithography according to the present embodiment is not particularly limited, and is preferably 0 to 50 parts by mass, more preferably 0 to 40 parts by mass, based on 100 parts by mass of the maleimide compound in the material for forming a film for lithography. By setting the above preferable range, the crosslinking reaction tends to be improved, and the occurrence of the mixing phenomenon with the resist layer tends to be suppressed.
< basic Compound >
Further, the composition for forming a lower layer film for lithography according to the present embodiment may contain a basic compound from the viewpoint of improving storage stability and the like.
The basic compound functions as a quencher for an acid to prevent a crosslinking reaction from proceeding by a trace amount of an acid generated from an acid generator. Such a basic compound is not limited to the following, and examples thereof include primary, secondary or tertiary aliphatic amines, mixed amines, aromatic amines, heterocyclic amines, nitrogen-containing compounds having a carboxyl group, nitrogen-containing compounds having a sulfonyl group, nitrogen-containing compounds having a hydroxyl group, nitrogen-containing compounds having a hydroxyphenyl group, alcoholic nitrogen-containing compounds, amide derivatives or imide derivatives, which are described in international publication No. 2013-024779.
The content of the basic compound in the composition for forming a film for lithography according to the present embodiment is not particularly limited, and is preferably 0 to 2 parts by mass, more preferably 0 to 1 part by mass, based on 100 parts by mass of the maleimide compound in the material for forming a film for lithography. By setting the above preferable range, the storage stability tends to be improved without excessively impairing the crosslinking reaction.
The composition for forming a film for lithography according to the present embodiment may contain known additives. The known additives are not limited to the following, and examples thereof include an ultraviolet absorber, an antifoaming agent, a coloring agent, a pigment, a nonionic surfactant, an anionic surfactant, and a cationic surfactant.
[ methods for Forming underlayer film and resist Pattern for lithography ]
The underlayer film for lithography of the present embodiment is formed using the composition for forming a film for lithography of the present embodiment.
In addition, the resist pattern forming method of the present embodiment includes the steps of: a step (A-1) of forming an underlayer film on a substrate using the composition for forming a film for lithography according to the present embodiment; a step (A-2) of forming at least 1 photoresist layer on the underlayer film; and a step (A-3) of irradiating a predetermined region of the photoresist layer with radiation and developing the photoresist layer after the step (A-2).
Further, one of the embodiments is a pattern forming method including the steps of: a step (B-1) of forming an underlayer film on a substrate using the composition for forming a film for lithography according to the present embodiment; a step (B-2) of forming an intermediate layer film on the underlayer film by using a resist intermediate layer film material containing silicon atoms; a step (B-3) of forming at least 1 photoresist layer on the intermediate layer film; a step (B-4) of irradiating a predetermined region of the photoresist layer with radiation and developing the same to form a resist pattern, after the step (B-3); and (B-5) etching the intermediate layer film using the resist pattern as a mask, etching the lower layer film using the obtained intermediate layer film pattern as an etching mask, and etching the substrate using the obtained lower layer film pattern as an etching mask, thereby forming a pattern on the substrate after the step (B-4).
The lower layer film for lithography according to the present embodiment is not particularly limited as long as it is formed from the composition for forming a film for lithography according to the present embodiment, and a known method can be applied. For example, the underlayer coating can be formed by applying the composition for forming a film for lithography of the present embodiment onto a substrate by a known coating method such as spin coating or screen printing, or by a printing method, and then removing the composition by evaporation of an organic solvent.
In the formation of the lower layer film, baking is preferably performed in order to suppress the occurrence of a mixing phenomenon with the upper layer resist and to promote a crosslinking reaction. In this case, the baking temperature is not particularly limited, but is preferably in the range of 80 to 450 ℃, and more preferably 200 to 400 ℃. The baking time is not particularly limited, and is preferably within a range of 10 to 300 seconds. The thickness of the underlayer film is not particularly limited, and may be suitably selected depending on the required performance, but is usually preferably 30 to 20000nm, more preferably 50 to 15000nm, and still more preferably 50 to 1000 nm.
Preferably, after the formation of the underlayer film on the substrate, a silicon-containing resist layer or a single-layer resist layer made of a normal hydrocarbon is formed thereon in the case of the 2-layer process, and a silicon-containing intermediate layer and a single-layer resist layer not containing silicon are formed thereon in the case of the 3-layer process. In this case, a known material can be used as a photoresist material for forming the resist layer.
As the silicon-containing resist material for the 2-layer process, it is preferable to use a silicon atom-containing polymer such as a polysilsesquioxane derivative or a vinylsilane derivative as a base polymer from the viewpoint of resistance to oxygen gas etching, and further use a positive type resist material containing an organic solvent, an acid generator, and if necessary, a basic compound. As the polymer containing silicon atoms, known polymers used for such resist materials can be used.
As a silicon-containing intermediate layer for a 3-layer process, a polysilsesquioxane based intermediate layer is preferably used. By providing the intermediate layer with an effect as an antireflection film, reflection tends to be effectively suppressed. For example, in the 193nm exposure process, when a material containing a large amount of aromatic groups and having high substrate etching resistance is used as the lower layer film, the k value tends to be high and the substrate reflection tends to be high, and the substrate reflection can be reduced to 0.5% or less by suppressing the reflection by the intermediate layer. Such an intermediate layer having an antireflection effect is not limited to the following, but for 193nm exposure, polysilsesquioxane which is crosslinked by an acid or heat and into which a phenyl group or a light-absorbing group having a silicon-silicon bond is introduced is preferably used.
In addition, an intermediate layer formed by a Chemical Vapor Deposition (CVD) method may also be used. The intermediate layer having a high effect as an antireflection film produced by the CVD method is not limited to the following, and for example, a SiON film is known. In general, compared to CVD, formation of an intermediate layer by a wet process such as spin coating or screen printing is simple and cost-effective. In the 3-layer process, the upper layer resist may be either a positive type or a negative type, and the same resist as a commonly used single layer resist may be used.
Further, the underlayer coating of the present embodiment can also be used as an antireflection coating for a normal single-layer resist or a base material for suppressing pattern collapse. The lower layer film of the present embodiment is excellent in etching resistance for substrate processing, and therefore can be expected to function as a hard mask for substrate processing.
When the resist layer is formed of the photoresist material, a wet process such as spin coating or screen printing is preferably used as in the case of forming the underlayer film. After the resist material is applied by a spin coating method or the like, a prebaking is usually performed, and the prebaking is preferably performed at 80 to 180 ℃ for 10 to 300 seconds. Thereafter, exposure was performed by a conventional method, and post-exposure baking (PEB) and development were performed to obtain a resist pattern. The thickness of the resist film is not particularly limited, but is preferably 30 to 500nm, more preferably 50 to 400 nm.
The exposure light may be appropriately selected and used according to the photoresist material used. Generally, high-energy radiation having a wavelength of 300nm or less is included, and specifically, excimer laser beams of 248nm, 193nm and 157nm, soft X-rays of 3 to 20nm, electron beams, X-rays and the like are included.
The resist pattern formed by the above method can suppress pattern collapse by the underlayer film of this embodiment. Therefore, by using the lower layer film of the present embodiment, a finer pattern can be obtained, and the amount of exposure required for obtaining the resist pattern can be reduced.
Next, the resulting resist pattern is used as a mask to perform etching. As the etching of the lower layer film in the 2-layer process, gas etching is preferably used. As the gas etching, etching using oxygen is suitable. In addition to oxygen, inert gas such as He or Ar, CO or CO may be added2、NH3、SO2、N2、NO2、H2A gas. Alternatively, only CO or CO may be used without using oxygen2、NH3、N2、NO2、H2The gas performs gas etching. In particular, the latter gas is preferably used for sidewall protection in order to prevent undercutting of the pattern sidewalls.
On the other hand, in the etching of the intermediate layer in the 3-layer process, gas etching is also preferably used. The gas etching can be applied to the same gas etching as the gas etching described in the 2-layer process. In particular, in the 3-layer process, the intermediate layer is preferably processed using a freon gas with the resist pattern as a mask. Thereafter, as described above, the lower layer film can be processed by, for example, oxygen etching using the intermediate layer pattern as a mask.
Here, when an inorganic hard mask intermediate layer film is formed as the intermediate layer, a silicon oxide film, a silicon nitride film, or a silicon oxynitride film (SiON film) is formed by a CVD method, an ALD method, or the like. The method for forming the nitride film is not limited to the following, and for example, the methods described in Japanese patent laid-open publication No. 2002-334869 (patent document 6) and WO2004/066377 (patent document 7) can be used. A photoresist film may be formed directly on the intermediate layer film, or an organic anti-reflection film (BARC) may be formed on the intermediate layer film by spin coating and a photoresist film may be formed thereon.
As the intermediate layer, a polysilsesquioxane-based intermediate layer is also preferably used. By providing the resist interlayer film with an effect as an antireflection film, reflection tends to be effectively suppressed. Specific materials for the polysilsesquioxane-based intermediate layer are not limited to the following, and for example, materials described in japanese patent laid-open nos. 2007 & 226170 (patent document 8) and 2007 & 226204 (patent document 9) can be used.
In addition, the subsequent etching of the substrate can also be carried out by conventional methods, for example, the substrate is SiO2In the case of SiN, etching mainly with a Freon gas is possible, and in the case of p-Si, Al, or W, etching mainly with a chlorine-based or bromine-based gas is possible. When a substrate is etched with a freon gas, a silicon-containing resist in a 2-layer resist process and a silicon-containing intermediate layer in a 3-layer process are peeled off simultaneously with the substrate processing. On the other hand, in the case of etching the substrate with a chlorine-based or bromine-based gas, the silicon-containing resist layer or the silicon-containing intermediate layer is peeled off separately, and usually, dry etching peeling by a freon-based gas is performed after the substrate processing.
The lower layer film of the present embodiment is characterized in that these substrates have excellent etching resistance. The substrate is not particularly limited, and known substrates can be suitably selected and used, and examples thereof include Si, α -Si, p-Si, and SiO2SiN, SiON, W, TiN, Al, etc. The substrate may be a laminate having a film to be processed (substrate to be processed) on a base material (support). Examples of such a film to be processed include Si and SiO2Various Low-k films such as SiON, SiN, p-Si, α -Si, W-Si, Al, Cu, and Al-Si, barrier films thereof, and the like are generally made of materials different from the substrate (support). The thickness of the substrate or the film to be processed is not particularly limited, but is preferably about 50 to 1000000nm, and more preferably 75 to 500000 nm.
Examples
The present invention will be described in more detail below by way of synthesis examples, production examples, and comparative examples, but the present invention is not limited to these examples at all.
[ molecular weight ]
The molecular weight of the synthesized compound was measured by LC-MS analysis using Acquisty UPLC/MALDI-Synapt HDMS manufactured by Water.
[ evaluation of Heat resistance ]
About 5mg of the sample was placed in an unsealed container made of aluminum using an EXSTAR6000TG-DTA apparatus made by SII Nanotechnology Inc., and heated to 500 ℃ at a heating rate of 10 ℃/min in a stream of nitrogen (100 ml/min), thereby measuring the amount of thermal weight loss. From the practical viewpoint, the following evaluation a or B is preferable. When the evaluation is A or B, the alloy has high heat resistance and can be applied to high-temperature baking.
< evaluation criteria >
A: the weight loss of the product at 400 ℃ is less than 10 percent
B: the heat weight reduction amount at 400 ℃ is 10 to 25 percent
C: the weight loss of the product at 400 ℃ is more than 25 percent
[ evaluation of solubility ]
Propylene Glycol Monomethyl Ether Acetate (PGMEA) and the compound and/or the resin were put into a 50ml screw-top bottle, stirred at 23 ℃ for 1 hour by a magnetic stirrer, and then the amount of the compound and/or the resin dissolved in PGMEA was measured, and the results were evaluated according to the following criteria. From the practical viewpoint, the following S, A or B evaluation is preferable. The resin composition of the present invention has high storage stability in a solution state for evaluation at S, A or B, and can be sufficiently used for edge bead filler rinse solutions (PGME/PGMEA mixtures) widely used in semiconductor microfabrication processes.
< evaluation criteria >
S: 15% by mass or more and less than 35% by mass
A: 5 to less than 15% by mass
B: less than 5% by mass
(Synthesis example 1) Synthesis of BAPP citraconic Maleimide
A100 ml container having an inner volume provided with a stirrer, a condenser tube and a burette was prepared. Into the vessel, 4.10g (10.0mmol) of 2, 2-bis [4- (4-aminophenoxy) phenyl ] propane (product name: BAPP, manufactured by Hill Seikagaku Kogyo Co., Ltd.), 2.07g (20.0mmol) of citraconic anhydride (manufactured by Kanto Kagaku Kogyo Co., Ltd.), 2.07g (20.0mmol) of maleic anhydride (manufactured by Kanto Kagaku Kogyo Co., Ltd.), 30ml of dimethylformamide and 60ml of toluene were charged, and 0.4g (2.3mmol) of p-toluenesulfonic acid and 0.1g of BHT (inhibitor) were added to prepare a reaction solution. The reaction mixture was stirred at 120 ℃ for 5 hours to effect a reaction, and the resultant water was recovered in a dean-Stark trap under azeotropic dehydration. Subsequently, the reaction solution was cooled to 40 ℃ and then added dropwise to a beaker containing 300ml of distilled water to precipitate a product. After the obtained slurry solution was filtered, the residue was washed with acetone and subjected to separation and purification by column chromatography to obtain 3.8g of citraconic maleimide, which is an objective compound represented by the following formula.
Figure BDA0003066334200000371
It is noted that according to 400MHz-1The following peaks were observed by H-NMR, confirming that citraconic maleimide has the chemical structure of the above formula.
1H-NMR: (d-DMSO, internal standard TMS) δ (ppm) 7.0-7.3 (18.0H, Ph-H, ═ CH-), 6.8(1.0H, ═ CH-), 2.0(3.0H, — CH-), and3(citraconimide ring)), 1.7(6H, -CH)3)。
The molecular weight of the product obtained after the reaction was measured by the method described above, and the results were a mixture of 3 kinds of compounds 584 (citraconimide), 570 (bismaleimide), and 598 (biscitraconimide). The composition ratio (584 (citraconimide)/570 (bismaleimide)/598 (biscitraconimide)) was 50/25/25.
In the following examples, a single compound of citraconic maleimide was used to prepare a film-forming material for lithography.
In addition, in the following synthesis examples 2 to 4, a mixture of citraconic maleimide/bismaleimide/biscitraconic imide in a ratio of 50/25/25 was also obtained, but in the examples, a single compound of citraconic maleimide was used to prepare a material for forming a film for lithography.
(Synthesis example 2) Synthesis of APB-N citraconic Maleimide
A100 ml container having an inner volume provided with a stirrer, a condenser tube and a burette was prepared. Into the vessel, 2.92g (10.0mmol) of 3, 3' - (1, 3-phenylenebis) oxydianiline (product name: APB-N, manufactured by Mitsui Fine Chemicals, Inc.), 2.07g (20.0mmol) of citraconic anhydride (manufactured by Kanto chemical Co., Ltd.), 2.07g (20.0mmol) of maleic anhydride (manufactured by Kanto chemical Co., Ltd.), 30ml of dimethylformamide and 60ml of toluene were charged, and 0.4g (2.3mmol) of p-toluenesulfonic acid and 0.1g of a polymerization inhibitor BHT were added to prepare a reaction solution. The reaction mixture was stirred at 110 ℃ for 5 hours to effect a reaction, and the resultant water was recovered in a dean-Stark trap under azeotropic dehydration. Subsequently, the reaction solution was cooled to 40 ℃ and then added dropwise to a beaker containing 300ml of distilled water to precipitate a product. The resulting slurry solution was filtered, and the residue was washed with methanol and subjected to separation and purification by column chromatography to obtain 3.52g of a target compound (APB-N citraconic maleimide) represented by the following formula.
Figure BDA0003066334200000381
It is noted that according to 400MHz-1The following peaks were observed by H-NMR, and the chemical structure of the above formula was confirmed.
1H-NMR: (d-DMSO, internal standard TMS) δ (ppm) 6.8-7.3 (12H, Ph-H), 7.0(3H, -CH ═ C), 2.1(3H, C-CH ═ C), and3). The molecular weight of the obtained compound was determined by the method described above, and the result was 466.
(Synthesis example 3) Synthesis of HFBAPP citraconic Maleimide
A100 ml container having an inner volume provided with a stirrer, a condenser tube and a burette was prepared. Into the vessel, 5.18g (10.0mmol) of 2, 2-bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane (product name: HFBAPP, manufactured by Hill Seikagaku Kogyo Co., Ltd.), 2.27g (22.0mmol) of citraconic anhydride (manufactured by Kanto Kagaku Kogyo Co., Ltd.), 2.27g (22.0mmol) of maleic anhydride (manufactured by Kanto Kagaku Kogyo Co., Ltd.), 30ml of dimethylformamide and 60ml of toluene were charged, and 0.4g (2.3mmol) of p-toluenesulfonic acid and 0.1g of polymerization inhibitor BHT0.1g were added to prepare a reaction solution. The reaction mixture was stirred at 110 ℃ for 5.0 hours to effect a reaction, and the resultant water was recovered in a dean-Stark trap under azeotropic dehydration. Subsequently, the reaction solution was cooled to 40 ℃ and then added dropwise to a beaker containing 300ml of distilled water to precipitate a product. After the obtained slurry solution was filtered, the residue was washed with methanol and subjected to separation and purification by column chromatography to obtain 3.9g of a target compound (HFBAPP citraconic maleimide) represented by the following formula.
Figure BDA0003066334200000391
It is noted that according to 400MHz-1The following peaks were observed by H-NMR, and the chemical structure of the above formula was confirmed.
1H-NMR: (d-DMSO, internal standard TMS) delta (ppm) 6.6-7.35 (16H, Ph-H), 2.1(3H, C-CH)3)、6.4(3H，-CH＝CH-)。
The molecular weight of the obtained compound was measured by the method described above, and the result was 691.
(Synthesis example 4) Synthesis of BisAP citraconic Maleimide
A100 ml container having an inner volume provided with a stirrer, a condenser tube and a burette was prepared. Into the vessel, 5.18g (10.0mmol) of 1, 4-bis [2- (4-aminophenyl) -2-propyl ] benzene (product name: Bisaniline-P, Mitsui Fine Chemicals, Inc.), 2.27g (22.0mmol) of citraconic anhydride (manufactured by Kanto chemical Co., Ltd.), 2.27g (22.0mmol) of maleic anhydride (manufactured by Kanto chemical Co., Ltd.), 30ml of dimethylformamide and 60ml of toluene were charged, and 0.4g (2.3mmol) of P-toluenesulfonic acid and 0.1g of a polymerization inhibitor and 0.1g of BHT were added to prepare a reaction solution. The reaction mixture was stirred at 110 ℃ for 6.0 hours to effect a reaction, and the resultant water was recovered in a dean-Stark trap under azeotropic dehydration. Subsequently, the reaction solution was cooled to 40 ℃ and then added dropwise to a beaker containing 300ml of distilled water to precipitate a product. The resulting slurry solution was filtered, and the residue was washed with methanol and subjected to separation and purification by column chromatography to obtain 4.2g of a target compound (BisAP citraconic maleimide) represented by the following formula.
Figure BDA0003066334200000401
It is noted that according to 400MHz-1The following peaks were observed by H-NMR, and the chemical structure of the above formula was confirmed.
1H-NMR: (d-DMSO, internal standard TMS) δ (ppm) 6.8-7.35 (12H, Ph-H), 6.7(3H, -CH ═ C), 2.1(3H, C-CH ═ C), and methods of making and using the same3)、1.6～1.7(12H，-C(CH3)2)。
The molecular weight of the obtained compound was measured by the method described above, and the result was 517.
(Synthesis example 5) Synthesis of BMI citraconic Maleimide resin
A100 ml container having an inner volume provided with a stirrer, a condenser tube and a burette was prepared. Into this vessel, 2.4g of diaminodiphenylmethane oligomer obtained in Synthesis example 1 of Japanese patent application laid-open No. 2001-26571, a mixture (22.0mmol/22.0mmol) of citraconic anhydride and maleic anhydride, 40ml of dimethylformamide and 60ml of toluene were charged, and 0.4g (2.3mmol) of p-toluenesulfonic acid and 0.1g of a polymerization inhibitor BHT were added to prepare a reaction solution. The reaction mixture was stirred at 110 ℃ for 8.0 hours to effect a reaction, and the resultant water was recovered in a dean-Stark trap under azeotropic dehydration. Subsequently, the reaction solution was cooled to 40 ℃ and then added dropwise to a beaker containing 300ml of distilled water to precipitate a product. After the obtained slurry solution was filtered, the residue was washed with methanol to obtain 4.6g of BMI citraconic maleimide resin.
(Synthesis example 6) Synthesis of BAN citraconic Maleimide resin
A100 ml container having an inner volume provided with a stirrer, a condenser tube and a burette was prepared. Into the vessel, 6.30g of biphenylaralkyl polyaniline resin (product name: BAN, manufactured by Nippon chemical Co., Ltd.), a mixture of citraconic anhydride and maleic anhydride (22.0mmol/22.0mmol), 40ml of dimethylformamide and 60ml of toluene were charged, and 0.4g (2.3mmol) of p-toluenesulfonic acid and 0.1g of a polymerization inhibitor were added to prepare a reaction solution. The reaction mixture was stirred at 110 ℃ for 6.0 hours to effect a reaction, and the resultant water was recovered in a dean-Stark trap under azeotropic dehydration. Subsequently, the reaction solution was cooled to 40 ℃ and then added dropwise to a beaker containing 300ml of distilled water to precipitate a product. After the obtained slurry solution was filtered, the residue was washed with methanol and subjected to separation and purification by column chromatography to obtain 4.6g of BAN citraconic maleimide resin.
(Synthesis example 7) Synthesis of BMI citraconic Maleimide high molecular weight Polymer
In a 300mL flask, 30g of diaminodiphenylmethane oligomer (DDMO) obtained in the synthesis example 1 of Japanese patent application laid-open No. 2001-26571 was charged, and 60g of methyl ethyl ketone as a solvent was added and dissolved by heating to 60 ℃ to obtain a solution. The solution was adsorbed on neutral silica gel (manufactured by Kanto chemical Co., Ltd.), and a mixed solvent of ethyl acetate 20 mass%/hexane 80 mass% was developed by silica gel column chromatography to fractionate only the components having repeating units represented by the following formula, followed by concentration, vacuum drying and solvent removal to obtain 9.6g of a DDMO high molecular weight material.
Figure BDA0003066334200000411
(DDMO high molecular weight Polymer; wherein n represents an integer of 1 to 4)
In a 100ml container equipped with a stirrer, a condenser and a burette and having an internal volume, 4.0g of the diaminodiphenylmethane oligomer high molecular weight material, a mixture of citraconic anhydride and maleic anhydride (22.0mmol/22.0mmol), 40ml of dimethylformamide and 60ml of toluene were charged, and 0.4g (2.3mmol) of p-toluenesulfonic acid and 0.1g of a polymerization inhibitor BHT were added to prepare a reaction solution. The reaction mixture was stirred at 110 ℃ for 8.0 hours to effect a reaction, and the resultant water was recovered in a dean-Stark trap under azeotropic dehydration. Subsequently, the reaction solution was cooled to 40 ℃ and then added dropwise to a beaker containing 300ml of distilled water to precipitate a product. After the obtained slurry solution was filtered, the residue was washed with methanol to obtain 5.5g of BMI citraconic maleimide high molecular weight material.
(Synthesis example 8) Synthesis of BAN citraconic Maleimide high molecular weight Polymer
A300 mL flask was charged with 40g of biphenylaralkyl polyaniline resin (trade name: BAN, manufactured by Nippon chemical Co., Ltd.), 60g of methyl ethyl ketone was added as a solvent, and the mixture was heated to 60 ℃ and dissolved to obtain a solution. The solution was adsorbed on neutral silica gel (manufactured by Kanto chemical Co., Ltd.), and a mixed solvent of ethyl acetate 20 mass%/hexane 80 mass% was developed by silica gel column chromatography to fractionate only the components of the repeating unit represented by the following formula, followed by concentration, vacuum drying and solvent removal, whereby 11.6g of a BAN high molecular weight material was obtained.
Figure BDA0003066334200000421
(BAN high molecular weight material; wherein n represents an integer of 2 to 4)
Into a 100ml container equipped with a stirrer, a condenser and a burette and having an internal volume, 5.0g of the BAN high molecular weight material, a mixture of citraconic anhydride and maleic anhydride (22.0mmol/22.0mmol), 40ml of dimethylformamide and 60ml of toluene were charged, and 0.4g (2.3mmol) of p-toluenesulfonic acid and 0.1g of polymerization inhibitor BHT0 were added to prepare a reaction solution. The reaction mixture was stirred at 110 ℃ for 8.0 hours to effect a reaction, and the resultant water was recovered in a dean-Stark trap under azeotropic dehydration. Subsequently, the reaction solution was cooled to 40 ℃ and then added dropwise to a beaker containing 300ml of distilled water to precipitate a product. After the obtained slurry solution was filtered, the residue was washed with methanol to obtain 6.6g of a BAN citraconic maleimide high molecular weight material.
< example 1>
Using BAPP citraconic maleimide obtained in synthesis example 1, a film-forming material for lithography was formed.
The results of thermogravimetry are as follows: the weight loss in heat at 400 ℃ of the obtained film-forming material for lithography was less than 10% (evaluation A). Further, the solubility in PGMEA was evaluated, and as a result, it was 5 mass% or more and less than 15 mass% (evaluation a), and it was evaluated that the obtained film-forming material for lithography had sufficient solubility.
Using 5 parts by mass of BAPP citraconic maleimide obtained in synthetic example 1, that is, 5 parts by mass of the above-mentioned film-forming material for lithography, 95 parts by mass of Propylene Glycol Monomethyl Ether Acetate (PGMEA) as a solvent was added, and the mixture was stirred with a stirrer at room temperature for at least 3 hours or more to prepare a composition for film formation for lithography.
< example 2>
Using APB-N citraconic maleimide obtained in Synthesis example 2, a film-forming material for lithography was formed.
The results of thermogravimetry are as follows: the weight loss in heat at 400 ℃ of the obtained film-forming material for lithography was less than 10% (evaluation A). Further, the solubility in PGMEA was evaluated, and as a result, it was 5 mass% or more and less than 15 mass% (evaluation a), and it was evaluated that the obtained film-forming material for lithography had sufficient solubility.
A composition for forming a film for lithography was prepared in the same manner as in example 1.
< example 3>
Using HFBAPP citraconic maleimide obtained in synthesis example 3, a film-forming material for lithography was formed.
The results of thermogravimetry are as follows: the weight loss in heat at 400 ℃ of the obtained film-forming material for lithography was less than 10% (evaluation A). Further, the solubility in PGMEA was evaluated, and as a result, it was 5 mass% or more and less than 15 mass% (evaluation a), and it was evaluated that the obtained film-forming material for lithography had sufficient solubility.
A composition for forming a film for lithography was prepared in the same manner as in example 1.
< example 4>
Using the BisAP citraconic maleimide obtained in synthesis example 4, a film-forming material for lithography was formed.
The results of thermogravimetry are as follows: the weight loss in heat at 400 ℃ of the obtained film-forming material for lithography was less than 10% (evaluation A). Further, the solubility in PGMEA was evaluated, and as a result, it was 5 mass% or more and less than 15 mass% (evaluation a), and it was evaluated that the obtained film-forming material for lithography had sufficient solubility.
A composition for forming a film for lithography was prepared in the same manner as in example 1.
< example 5>
Using the BMI citraconic maleimide resin obtained in synthesis example 5, a film-forming material for lithography was formed.
The results of thermogravimetry are as follows: the weight loss in heat at 400 ℃ of the obtained film-forming material for lithography was less than 10% (evaluation A). Further, the solubility in PGMEA was evaluated, and as a result, it was 5 mass% or more and less than 15 mass% (evaluation a), and it was evaluated that the obtained film-forming material for lithography had sufficient solubility.
A composition for forming a film for lithography was prepared in the same manner as in example 1.
< example 5A >
Using the BMI citraconic maleimide high molecular weight material obtained in synthesis example 7, a film formation material for lithography was formed.
The results of thermogravimetry are as follows: the weight loss in heat at 400 ℃ of the obtained film-forming material for lithography was less than 10% (evaluation A). Further, the solubility in PGMEA was evaluated, and as a result, it was 5 mass% or more and less than 15 mass% (evaluation a), and it was evaluated that the obtained film-forming material for lithography had sufficient solubility.
A composition for forming a film for lithography was prepared in the same manner as in example 1.
< example 6>
Using the BAN citraconic maleimide resin obtained in synthesis example 6, a film-forming material for lithography was formed.
The results of thermogravimetry are as follows: the weight loss in heat at 400 ℃ of the obtained film-forming material for lithography was less than 10% (evaluation A). Further, the solubility in PGMEA was evaluated, and as a result, it was 5 mass% or more and less than 15 mass% (evaluation a), and it was evaluated that the obtained film-forming material for lithography had sufficient solubility.
A composition for forming a film for lithography was prepared in the same manner as in example 1.
< example 6A >
Using the BAN citraconic maleimide high molecular weight body obtained in synthesis example 8, a film formation material for lithography was formed.
The results of thermogravimetry are as follows: the weight loss in heat at 400 ℃ of the obtained film-forming material for lithography was less than 10% (evaluation A). Further, the solubility in PGMEA was evaluated, and as a result, it was 5 mass% or more and less than 15 mass% (evaluation a), and it was evaluated that the obtained film-forming material for lithography had sufficient solubility.
A composition for forming a film for lithography was prepared in the same manner as in example 1.
< example 7>
A material for forming a film for lithography was prepared by compounding 5 parts by mass of BAPP citraconic maleimide and 0.1 part by mass of TPIZ as a crosslinking accelerator.
The results of thermogravimetry are as follows: the weight loss in heat at 400 ℃ of the obtained film-forming material for lithography was less than 10% (evaluation A). Further, the solubility in PGMEA was evaluated, and as a result, it was 5 mass% or more and less than 15 mass% (evaluation a), and it was evaluated that the obtained film-forming material for lithography had sufficient solubility.
A composition for forming a film for lithography was prepared in the same manner as in example 1, except that the above-mentioned material for forming a film for lithography was used.
< example 8>
A material for forming a film for lithography was prepared by blending 5 parts by mass of APB-N citraconic maleimide and 0.1 part by mass of TPIZ as a crosslinking accelerator.
The results of thermogravimetry are as follows: the weight loss in heat at 400 ℃ of the obtained film-forming material for lithography was less than 10% (evaluation A). Further, the solubility in PGMEA was evaluated, and as a result, it was 5 mass% or more and less than 15 mass% (evaluation a), and it was evaluated that the obtained film-forming material for lithography had sufficient solubility.
A composition for forming a film for lithography was prepared in the same manner as in example 1, except that the above-mentioned material for forming a film for lithography was used.
< example 9>
The resulting film was compounded with 5 parts by mass of HFBAPP citraconic maleimide and 0.1 part by mass of TPIZ as a crosslinking accelerator to form a film-forming material for lithography.
The results of thermogravimetry are as follows: the weight loss in heat at 400 ℃ of the obtained film-forming material for lithography was less than 10% (evaluation A). Further, the solubility in PGMEA was evaluated, and as a result, it was 5 mass% or more and less than 15 mass% (evaluation a), and it was evaluated that the obtained film-forming material for lithography had sufficient solubility.
A composition for forming a film for lithography was prepared in the same manner as in example 1, except that the above-mentioned material for forming a film for lithography was used.
< example 10>
A material for forming a film for lithography was prepared by blending 5 parts by mass of BisAP citraconic maleimide and 0.1 part by mass of TPIZ as a crosslinking accelerator.
The results of thermogravimetry are as follows: the weight loss in heat at 400 ℃ of the obtained film-forming material for lithography was less than 10% (evaluation A). Further, the solubility in PGMEA was evaluated, and as a result, it was 5 mass% or more and less than 15 mass% (evaluation a), and it was evaluated that the obtained film-forming material for lithography had sufficient solubility.
A composition for forming a film for lithography was prepared in the same manner as in example 1, except that the above-mentioned material for forming a film for lithography was used.
< example 11>
A material for forming a film for lithography was formed by compounding 5 parts by mass of BMI citraconmaleimide resin and 0.1 part by mass of TPIZ as a crosslinking accelerator.
The results of thermogravimetry are as follows: the weight loss in heat at 400 ℃ of the obtained film-forming material for lithography was less than 10% (evaluation A). Further, the solubility in PGMEA was evaluated, and as a result, it was 5 mass% or more and less than 15 mass% (evaluation a), and it was evaluated that the obtained film-forming material for lithography had sufficient solubility.
A composition for forming a film for lithography was prepared in the same manner as in example 1, except that the above-mentioned material for forming a film for lithography was used.
< example 11A >
A material for forming a film for lithography was formed by compounding 5 parts by mass of a BMI citraconic maleimide high molecular weight material and 0.1 part by mass of TPIZ as a crosslinking accelerator.
The results of thermogravimetry are as follows: the weight loss in heat at 400 ℃ of the obtained film-forming material for lithography was less than 10% (evaluation A). Further, the solubility in PGMEA was evaluated, and as a result, it was 5 mass% or more and less than 15 mass% (evaluation a), and it was evaluated that the obtained film-forming material for lithography had sufficient solubility.
A composition for forming a film for lithography was prepared in the same manner as in example 1, except that the above-mentioned material for forming a film for lithography was used.
< example 12>
A material for forming a film for lithography was prepared by compounding 5 parts by mass of BAN citraconic maleimide resin and 0.1 part by mass of TPIZ as a crosslinking accelerator.
The results of thermogravimetry are as follows: the weight loss in heat at 400 ℃ of the obtained film-forming material for lithography was less than 10% (evaluation A). Further, the solubility in PGMEA was evaluated, and as a result, it was 5 mass% or more and less than 15 mass% (evaluation a), and it was evaluated that the obtained film-forming material for lithography had sufficient solubility.
A composition for forming a film for lithography was prepared in the same manner as in example 1, except that the above-mentioned material for forming a film for lithography was used.
< example 12A >
A film-forming material for lithography was formed by compounding 5 parts by mass of a BAN citraconic maleimide high-molecular weight material and 0.1 part by mass of TPIZ as a crosslinking accelerator.
The results of thermogravimetry are as follows: the weight loss in heat at 400 ℃ of the obtained film-forming material for lithography was less than 10% (evaluation A). Further, the solubility in PGMEA was evaluated, and as a result, it was 5 mass% or more and less than 15 mass% (evaluation a), and it was evaluated that the obtained film-forming material for lithography had sufficient solubility.
A composition for forming a film for lithography was prepared in the same manner as in example 1, except that the above-mentioned material for forming a film for lithography was used.
< example 13>
A film-forming material for lithography was formed by using 5 parts by mass of BAPP citraconic maleimide, 2 parts by mass of benzoxazine (BF-BXZ; manufactured by Mitsui chemical industries, Ltd.) represented by the following formula as a crosslinking agent, and 0.1 part by mass of 2,4, 5-Triphenylimidazole (TPIZ) as a crosslinking accelerator.
Figure BDA0003066334200000481
The results of thermogravimetry are as follows: the weight loss in heat at 400 ℃ of the obtained film-forming material for lithography was less than 10% (evaluation A). The solubility in PGMEA was evaluated, and as a result, it was 5 mass% or more and less than 15 mass% (evaluation a), and it was evaluated that the obtained material for forming a film for lithography had component solubility.
A composition for forming a film for lithography was prepared in the same manner as in example 1, except that the above-mentioned material for forming a film for lithography was used.
< example 14>
A film-forming material for lithography was formed by using 5 parts by mass of BAPP citraconic maleimide and 2 parts by mass of a biphenyl aralkyl type epoxy resin (NC-3000-L; manufactured by Nippon Kabushiki Kaisha) represented by the following formula as a crosslinking agent, and blending 0.1 part by mass of TPIZ as a crosslinking accelerator.
Figure BDA0003066334200000482
(in the formula, n is an integer of 1 to 4.)
(NC-3000-L)
The results of thermogravimetry are as follows: the weight loss in heat at 400 ℃ of the obtained film-forming material for lithography was less than 10% (evaluation A). The solubility in PGMEA was evaluated, and as a result, it was 5 mass% or more and less than 15 mass% (evaluation a), and it was evaluated that the obtained material for forming a film for lithography had component solubility.
A composition for forming a film for lithography was prepared in the same manner as in example 1, except that the above-mentioned material for forming a film for lithography was used.
< example 15>
A material for forming a film for lithography was formed by using 5 parts by mass of BAPP citraconic maleimide, 2 parts by mass of diallylbisphenol A type cyanate ester (DABPA-CN; manufactured by Mitsubishi gas chemical Co., Ltd.) represented by the following formula as a crosslinking agent, and 0.1 part by mass of 2,4, 5-Triphenylimidazole (TPIZ) as a crosslinking accelerator.
Figure BDA0003066334200000491
The results of thermogravimetry are as follows: the weight loss in heat at 400 ℃ of the obtained film-forming material for lithography was less than 10% (evaluation A). The solubility in PGMEA was evaluated, and as a result, it was 5 mass% or more and less than 15 mass% (evaluation a), and it was evaluated that the obtained material for forming a film for lithography had component solubility.
A composition for forming a film for lithography was prepared in the same manner as in example 1, except that the above-mentioned material for forming a film for lithography was used.
< example 16>
A film-forming material for lithography was formed by using 5 parts by mass of BAPP citraconic maleimide, 2 parts by mass of diallyl bisphenol A (BPA-CA; manufactured by Seikagaku chemical Co., Ltd.) represented by the following formula as a crosslinking agent, and 0.1 part by mass of 2,4, 5-Triphenylimidazole (TPIZ) as a crosslinking accelerator.
Figure BDA0003066334200000501
The results of thermogravimetry are as follows: the weight loss in heat at 400 ℃ of the obtained film-forming material for lithography was less than 10% (evaluation A). The solubility in PGMEA was evaluated, and as a result, it was 5 mass% or more and less than 15 mass% (evaluation a), and it was evaluated that the obtained material for forming a film for lithography had component solubility.
A composition for forming a film for lithography was prepared in the same manner as in example 1, except that the above-mentioned material for forming a film for lithography was used.
< example 17>
A material for forming a film for lithography was formed using 5 parts by mass of BAPP citraconic maleimide and 2 parts by mass of a diphenylmethane allyl phenol resin (APG-1, manufactured by Royal chemical industries, Ltd.) represented by the following formula as a crosslinking agent.
Figure BDA0003066334200000502
(in the formula, n is an integer of 1 to 3.)
(APG-1)
The results of thermogravimetry are as follows: the weight loss in heat at 400 ℃ of the obtained film-forming material for lithography was less than 10% (evaluation A). The solubility in PGMEA was evaluated, and as a result, it was 5 mass% or more and less than 15 mass% (evaluation a), and it was evaluated that the obtained material for forming a film for lithography had component solubility.
A composition for forming a film for lithography was prepared in the same manner as in example 1, except that the above-mentioned material for forming a film for lithography was used.
< example 18>
A material for forming a film for lithography was formed using 5 parts by mass of BAPP citraconic maleimide and 2 parts by mass of a diphenylmethane acryl-based phenol resin (APG-2, manufactured by Royal chemical industries, Ltd.) represented by the following formula as a crosslinking agent.
Figure BDA0003066334200000511
(in the formula, n is an integer of 1 to 3.)
(APG-2)
The results of thermogravimetry are as follows: the weight loss in heat at 400 ℃ of the obtained film-forming material for lithography was less than 10% (evaluation A). The solubility in PGMEA was evaluated, and as a result, it was 5 mass% or more and less than 15 mass% (evaluation a), and it was evaluated that the obtained material for forming a film for lithography had component solubility.
A composition for forming a film for lithography was prepared in the same manner as in example 1, except that the above-mentioned material for forming a film for lithography was used.
< example 19>
A material for forming a film for lithography was formed using 5 parts by mass of BAPP citraconic maleimide and 2 parts by mass of 4, 4' -diaminodiphenylmethane (DDM; manufactured by Tokyo chemical Co., Ltd.) represented by the following formula as a crosslinking agent.
Figure BDA0003066334200000512
The results of thermogravimetry are as follows: the weight loss in heat at 400 ℃ of the obtained film-forming material for lithography was less than 10% (evaluation A). The solubility in PGMEA was evaluated, and as a result, it was 5 mass% or more and less than 15 mass% (evaluation a), and it was evaluated that the obtained material for forming a film for lithography had component solubility.
A composition for forming a film for lithography was prepared in the same manner as in example 1, except that the above-mentioned material for forming a film for lithography was used.
< production example 1>
A four-necked flask having an internal volume of 10L and a detachable bottom, which was equipped with a serpentine condenser, a thermometer and a stirring blade, was prepared. In the four-necked flask, 1.09kg of 1, 5-dimethylnaphthalene (7mol, manufactured by Mitsubishi gas chemical corporation), 2.1kg of a 40 mass% formalin aqueous solution (28 mol in terms of formaldehyde, manufactured by Mitsubishi gas chemical corporation) and 0.97ml of 98 mass% sulfuric acid (manufactured by Kanto chemical corporation) were put into a nitrogen stream, and reacted for 7 hours under normal pressure and reflux at 100 ℃. Thereafter, 1.8kg of ethylbenzene (manufactured by Wako pure chemical industries, Ltd., reagent grade) was added as a diluting solvent to the reaction mixture, and after standing, the aqueous phase of the lower phase was removed. Further, neutralization and water washing were performed to distill off ethylbenzene and unreacted 1, 5-dimethylnaphthalene under reduced pressure, thereby obtaining 1.25kg of dimethylnaphthalene formaldehyde resin as a pale brown solid.
The molecular weight of the obtained dimethylnaphthalene formaldehyde resin was number average molecular weight (Mn): 562. weight average molecular weight (Mw): 1168. dispersity (Mw/Mn): 2.08.
next, a four-necked flask having an internal volume of 0.5L and equipped with a serpentine condenser, a thermometer and a stirring blade was prepared. Into the four-necked flask, 100g (0.51mol) of the dimethylnaphthalene formaldehyde resin obtained as described above and 0.05g of p-toluenesulfonic acid were charged under a nitrogen stream, heated to 190 ℃ for 2 hours, and then stirred. Then, 52.0g (0.36mol) of 1-naphthol was further added thereto, and the temperature was further raised to 220 ℃ to react for 2 hours. After the dilution with the solvent, neutralization and washing with water were carried out, and the solvent was removed under reduced pressure, whereby 126.1g of a modified resin (CR-1) was obtained as a dark brown solid.
The resin (CR-1) obtained was Mn: 885. mw: 2220. Mw/Mn of 2.51.
The results of Thermogravimetry (TG) are as follows: the weight loss at 400 ℃ of the obtained resin was more than 25% (evaluation C). Therefore, it was evaluated as difficult to use for high-temperature baking.
The solubility in PGMEA was evaluated, and as a result, the solubility was 10 mass% or more (evaluation a), and the solubility was evaluated to be sufficient.
The Mn, Mw and Mw/Mn were measured by Gel Permeation Chromatography (GPC) analysis under the following conditions to determine the molecular weight in terms of polystyrene.
The device comprises the following steps: shodex GPC-101 type (manufactured by Showa Denko K.K.)
Column: KF-80 MX 3
Eluent: THF 1 mL/min
Temperature: 40 deg.C
Preparation example 2 Synthesis of BAPP citraconimide
A100 ml container having an inner volume provided with a stirrer, a condenser tube and a burette was prepared. Into the vessel, 4.10g (10.0mmol) of 2, 2-bis [4- (4-aminophenoxy) phenyl ] propane (product name: BAPP, manufactured by Hill Seikagaku Kogyo Co., Ltd.), 4.15g (40.0mmol) of citraconic anhydride (manufactured by Kanto chemical Co., Ltd.), 30ml of dimethylformamide and 60ml of toluene were charged, and 0.4g (2.3mmol) of p-toluenesulfonic acid and 0.1g of BHT (inhibitor) were added to prepare a reaction solution. The reaction mixture was stirred at 120 ℃ for 5 hours to effect a reaction, and the resultant water was recovered in a dean-Stark trap under azeotropic dehydration. Subsequently, the reaction solution was cooled to 40 ℃ and then added dropwise to a beaker containing 300ml of distilled water to precipitate a product. After the obtained slurry solution was filtered, the residue was washed with acetone and subjected to separation and purification by column chromatography to obtain 3.76g of a target compound (BAPP citraconimide) represented by the following formula.
Figure BDA0003066334200000531
It is noted that according to 400MHz-1The following peaks were observed by H-NMR, and the chemical structure of the above formula was confirmed.
1H-NMR: (d-DMSO, internal standard TMS) δ (ppm) 6.8-7.4 (16H, Ph-H), 6.7(2H, -CH ═ C), 2.1(6H, C-CH ═ C), and3)、1.6(6H，-C(CH3)2). The molecular weight of the obtained compound was determined by the aforementioned method, and the result was 598.
Preparation example 3 Synthesis of APB-N citraconimide
A100 ml container having an inner volume provided with a stirrer, a condenser tube and a burette was prepared. Into the vessel, 2.92g (10.0mmol) of 3, 3' - (1, 3-phenylenebis) oxydianiline (product name: APB-N, manufactured by Mitsui Fine Chemicals, Inc.), 4.15g (40.0mmol) of citraconic anhydride (manufactured by Kanto chemical Co., Ltd.), 30ml of dimethylformamide and 60ml of toluene were charged, and 0.4g (2.3mmol) of p-toluenesulfonic acid and 0.1g of polymerization inhibitor BHT0 were added to prepare a reaction solution. The reaction mixture was stirred at 110 ℃ for 5 hours to effect a reaction, and the resultant water was recovered in a dean-Stark trap under azeotropic dehydration. Subsequently, the reaction solution was cooled to 40 ℃ and then added dropwise to a beaker containing 300ml of distilled water to precipitate a product. The resulting slurry solution was filtered, and the residue was washed with methanol and subjected to separation and purification by column chromatography to obtain 3.52g of a target compound (APB-N citraconimide) represented by the following formula.
Figure BDA0003066334200000541
It is noted that according to 400MHz-1The following peaks were observed by H-NMR, and the chemical structure of the above formula was confirmed.
1H-NMR: (d-DMSO, internal standard TMS) δ (ppm) 6.7-7.4 (12H, Ph-H), 6.4(2H, -CH ═ C), 2.2(6H, C-CH ═ C), and3). The molecular weight of the obtained compound was measured by the method described above, and the result was 480.
Preparation example 4 Synthesis of HFBAPP citraconimide
A100 ml container having an inner volume provided with a stirrer, a condenser tube and a burette was prepared. Into the vessel, 5.18g (10.0mmol) of 2, 2-bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane (product name: HFBAPP, manufactured by Hill Seikagaku Kogyo Co., Ltd.), 4.56g (44.0mmol) of citraconic anhydride (manufactured by Kanto chemical Co., Ltd.), 30ml of dimethylformamide and 60ml of toluene were charged, and 0.4g (2.3mmol) of p-toluenesulfonic acid and 0.1g of BHT (inhibitor) were added to prepare a reaction solution. The reaction mixture was stirred at 110 ℃ for 5.0 hours to effect a reaction, and the resultant water was recovered in a dean-Stark trap under azeotropic dehydration. Subsequently, the reaction solution was cooled to 40 ℃ and then added dropwise to a beaker containing 300ml of distilled water to precipitate a product. After the obtained slurry solution was filtered, the residue was washed with methanol and subjected to separation and purification by column chromatography to obtain 3.9g of a target compound (HFBAPP citraconimide) represented by the following formula.
Figure BDA0003066334200000551
It is noted that according to 400MHz-1The following peaks were observed by H-NMR, and the chemical structure of the above formula was confirmed.
1H-NMR: (d-DMSO, internal standard TMS) δ (ppm) 6.6-7.3 (16H, Ph-H), 6.4(2H, -CH ═ C), 2.2(6H, C-CH ═ C), and3)。
the molecular weight of the obtained compound was measured by the method described above, and the result was 706.
Preparation example 5 Synthesis of BisAP citraconimide
A100 ml container having an inner volume provided with a stirrer, a condenser tube and a burette was prepared. Into the vessel, 5.18g (10.0mmol) of 1, 4-bis [2- (4-aminophenyl) -2-propyl ] benzene (product name: Bisaniline-P, Mitsui Fine Chemicals, Inc.), 4.56g (44.0mmol) of citraconic anhydride (manufactured by Kanto chemical Co., Ltd.), 30ml of dimethylformamide and 60ml of toluene were charged, and 0.4g (2.3mmol) of P-toluenesulfonic acid and 0.1g of BHT (polymerization inhibitor) were added to prepare a reaction solution. The reaction mixture was stirred at 110 ℃ for 6.0 hours to effect a reaction, and the resultant water was recovered in a dean-Stark trap under azeotropic dehydration. Subsequently, the reaction solution was cooled to 40 ℃ and then added dropwise to a beaker containing 300ml of distilled water to precipitate a product. The resulting slurry solution was filtered, and the residue was washed with methanol and subjected to separation and purification by column chromatography to obtain 4.2g of a target compound (BisAP citraconimide) represented by the following formula.
Figure BDA0003066334200000561
It is noted that according to 400MHz-1The following peaks were observed by H-NMR, and the chemical structure of the above formula was confirmed.
1H-NMR: (d-DMSO, internal standard TMS) δ (ppm) 6.8-7.4 (12H, Ph-H), 6.7(2H, -CH ═ C), 2.1(6H, C-CH ═ C), and3)、1.6～1.7(12H，-C(CH3)2). The molecular weight of the obtained compound was measured by the aforementioned method, and the result was 532.
Preparation example 6 Synthesis of BMI citraconimide resin
A100 ml container having an inner volume provided with a stirrer, a condenser tube and a burette was prepared. Into this vessel, 2.4g of diaminodiphenylmethane oligomer obtained in Synthesis example 1 of Japanese patent application laid-open No. 2001-26571, 4.56g (44.0mmol) of citraconic anhydride (manufactured by Kanto chemical Co., Ltd.), 40ml of dimethylformamide and 60ml of toluene were charged, and 0.4g (2.3mmol) of p-toluenesulfonic acid and 0.1g of BHT as a polymerization inhibitor were added to prepare a reaction solution. The reaction mixture was stirred at 110 ℃ for 8.0 hours to effect a reaction, and the resultant water was recovered in a dean-Stark trap under azeotropic dehydration. Subsequently, the reaction solution was cooled to 40 ℃ and then added dropwise to a beaker containing 300ml of distilled water to precipitate a product. After the obtained slurry solution was filtered, the residue was washed with methanol to obtain 4.7g of citraconimide resin (BMI citraconimide resin) represented by the following formula.
Figure BDA0003066334200000562
(wherein n represents an integer of 0 to 4.)
The molecular weight was measured by the method described above, and the result was 446.
Preparation example 7 Synthesis of BAN citraconimide resin
A100 ml container having an inner volume provided with a stirrer, a condenser tube and a burette was prepared. Into the vessel, 6.30g of biphenylaralkyl polyaniline resin (product name: BAN, manufactured by Nippon chemical Co., Ltd.), 4.56g (44.0mmol) of citraconic anhydride (manufactured by Kanto chemical Co., Ltd.), 40ml of dimethylformamide and 60ml of toluene were charged, and 0.4g (2.3mmol) of p-toluenesulfonic acid and 0.1g of BHT (polymerization inhibitor) were added to prepare a reaction solution. The reaction mixture was stirred at 110 ℃ for 6.0 hours to effect a reaction, and the resultant water was recovered in a dean-Stark trap under azeotropic dehydration. Subsequently, the reaction solution was cooled to 40 ℃ and then added dropwise to a beaker containing 300ml of distilled water to precipitate a product. After the obtained slurry solution was filtered, the residue was washed with methanol, and subjected to separation and purification by column chromatography to obtain 5.5g of a target compound represented by the following formula (BAN citraconimide resin).
Figure BDA0003066334200000571
(wherein n represents an integer of 1 to 4.)
< comparative example 1>
A film-forming material for lithography was prepared by blending 0.1 parts by mass of TPIZ as a crosslinking accelerator with 2 parts by mass of CR-15 parts by mass of a biphenylaralkyl type epoxy resin represented by the following formula (NC-3000-L; manufactured by Nippon chemical Co., Ltd.) as a crosslinking agent.
A composition for forming a film for lithography was prepared in the same manner as in example 1, except that the above-mentioned material for forming a film for lithography was used.
< comparative example 2>
Using CR-1, a material for forming a film for lithography was formed.
A composition for forming a film for lithography was prepared in the same manner as in example 1, except that the above-mentioned material for forming a film for lithography was used.
< comparative example 3>
Using BAPP citraconimide, a film-forming material for lithography was formed.
The results of thermogravimetry are as follows: the weight loss in heat at 400 ℃ of the obtained film-forming material for lithography was less than 10% (evaluation A). Further, the solubility in PGMEA was evaluated, and as a result, it was 15 mass% or more and less than 35 mass% (evaluation S), and it was evaluated that the obtained film-forming material for lithography had sufficient solubility.
A composition for forming a film for lithography was prepared in the same manner as in example 1.
< comparative example 4>
The material for forming a film for lithography was formed using APB-N citraconimide.
The results of thermogravimetry are as follows: the weight loss in heat at 400 ℃ of the obtained film-forming material for lithography was less than 10% (evaluation A). Further, the solubility in PGMEA was evaluated, and as a result, it was 15 mass% or more and less than 35 mass% (evaluation S), and it was evaluated that the obtained film-forming material for lithography had sufficient solubility.
A composition for forming a film for lithography was prepared in the same manner as in example 1.
< comparative example 5>
Using HFBAPP citraconimide, a film-forming material for lithography was formed.
The results of thermogravimetry are as follows: the weight loss in heat at 400 ℃ of the obtained film-forming material for lithography was less than 10% (evaluation A). Further, the solubility in PGMEA was evaluated, and as a result, it was 15 mass% or more and less than 35 mass% (evaluation S), and it was evaluated that the obtained film-forming material for lithography had sufficient solubility.
A composition for forming a film for lithography was prepared in the same manner as in example 1.
< comparative example 6>
Using BisAP citraconimide, a film-forming material for lithography was formed.
The results of thermogravimetry are as follows: the weight loss in heat at 400 ℃ of the obtained film-forming material for lithography was less than 10% (evaluation A). Further, the solubility in PGMEA was evaluated, and as a result, it was 15 mass% or more and less than 35 mass% (evaluation S), and it was evaluated that the obtained film-forming material for lithography had sufficient solubility.
A composition for forming a film for lithography was prepared in the same manner as in example 1.
< comparative example 7>
Using BMI citraconimide resin, a film-forming material for lithography was formed.
The results of thermogravimetry are as follows: the weight loss in heat at 400 ℃ of the obtained film-forming material for lithography was less than 10% (evaluation A). Further, the solubility in PGMEA was evaluated, and as a result, it was 5 mass% or more and less than 15 mass% (evaluation a), and it was evaluated that the obtained film-forming material for lithography had sufficient solubility.
A composition for forming a film for lithography was prepared in the same manner as in example 1.
< comparative example 8>
Using BAM citraconimide resin, a film-forming material for lithography was formed.
The results of thermogravimetry are as follows: the weight loss in heat at 400 ℃ of the obtained film-forming material for lithography was less than 10% (evaluation A). Further, the solubility in PGMEA was evaluated, and as a result, it was 5 mass% or more and less than 15 mass% (evaluation a), and it was evaluated that the obtained film-forming material for lithography had sufficient solubility.
A composition for forming a film for lithography was prepared in the same manner as in example 1.
< comparative example 9>
A material for forming a film for lithography was formed using a phenylmethaneimide oligomer (BMI oligomer; BMI-2300, Mass. chemical industry) represented by the following formula.
Figure BDA0003066334200000591
(in the formula, n is an integer of 0 to 4.)
(BMI-2300)
The results of thermogravimetry are as follows: the weight loss in heat at 400 ℃ of the obtained film-forming material for lithography was less than 10% (evaluation A). Further, the solubility in PGMEA was evaluated, and as a result, it was 5 mass% or more and less than 15 mass% (evaluation a), and it was evaluated that the obtained film-forming material for lithography had sufficient solubility. A composition for forming a film for lithography was prepared in the same manner as in example 1.
< comparative example 10>
As the bismaleimide compound, bismaleimide represented by the following formula (BMI-80; K.I Chemical Industry Co., LTD.) was used to form a material for forming a film for lithography.
Figure BDA0003066334200000601
The results of thermogravimetry are as follows: the weight loss in heat at 400 ℃ of the obtained film-forming material for lithography was less than 10% (evaluation A). Further, the solubility in PGMEA was evaluated, and as a result, it was 5 mass% or more and less than 15 mass% (evaluation a), and it was evaluated that the obtained film-forming material for lithography had sufficient solubility.
A composition for forming a film for lithography was prepared in the same manner as in example 1.
< example 20>
A material for forming a film for lithography was prepared by blending 5 parts by mass of BAPP citraconic maleimide and 0.1 part by mass of Irgacure184 (manufactured by BASF corporation) represented by the following formula as a photopolymerization initiator.
To 5 parts by mass of the above-mentioned film-forming material for lithography, 95 parts by mass of PGMEA as a solvent was added, and the mixture was stirred at room temperature for at least 3 hours or more with a stirrer, thereby preparing a film-forming composition for lithography.
Figure BDA0003066334200000602
< example 21>
A material for forming a film for lithography was prepared by blending 5 parts by mass of APB-N citraconic maleimide and 0.1 part by mass of Irgacure184 (manufactured by BASF corporation) as a photopolymerization initiator.
A composition for forming a film for lithography was prepared in the same manner as in example 20.
< example 22>
The resulting composition was compounded with 5 parts by mass of HFBAPP citraconic maleimide and 0.1 part by mass of Irgacure184 (manufactured by BASF corporation) as a photopolymerization initiator to prepare a film-forming material for lithography.
A composition for forming a film for lithography was prepared in the same manner as in example 20.
< example 23>
The material was prepared by mixing 5 parts by mass of BisAP citraconmaleimide and 0.1 part by mass of Irgacure184 (manufactured by BASF corporation) as a photopolymerization initiator.
A composition for forming a film for lithography was prepared in the same manner as in example 20.
< example 24>
A material for forming a film for lithography was prepared by mixing 5 parts by mass of BMI citraconmaleimide resin and 0.1 part by mass of Irgacure184 (manufactured by BASF corporation) as a photopolymerization initiator.
A composition for forming a film for lithography was prepared in the same manner as in example 20.
< example 24A >
A material for forming a film for lithography was prepared by blending 5 parts by mass of a high molecular weight polymer of citraconic maleimide (BMI) and 0.1 part by mass of Irgacure184 (manufactured by BASF corporation) as a photopolymerization initiator.
A composition for forming a film for lithography was prepared in the same manner as in example 20.
< example 25>
A material for forming a film for lithography was prepared by mixing 5 parts by mass of BAN citraconic maleimide resin and 0.1 part by mass of Irgacure184 (manufactured by BASF corporation) as a photopolymerization initiator.
A composition for forming a film for lithography was prepared in the same manner as in example 20.
< example 25A >
A material for forming a film for lithography was prepared by mixing 5 parts by mass of BAN citraconic maleimide high-molecular weight material and 0.1 part by mass of Irgacure184 (manufactured by BASF corporation) as a photopolymerization initiator.
A composition for forming a film for lithography was prepared in the same manner as in example 20.
< example 26>
A film-forming material for lithography was formed by using 5 parts by mass of BAPP citraconic maleimide and 0.1 part by mass of Irgacure184 (manufactured by BASF corporation) as a photo-radical polymerization initiator in combination with BF-BXZ 2 parts by mass as a crosslinking agent.
A composition for forming a film for lithography was prepared in the same manner as in example 20.
< example 27>
A material for forming a film for lithography was formed by using 5 parts by mass of BAPP citraconic maleimide and 2 parts by mass of NC-3000-L as a crosslinking agent, and 0.1 part by mass of Irgacure184 (manufactured by BASF corporation) as a photo radical polymerization initiator.
A composition for forming a film for lithography was prepared in the same manner as in example 20.
< example 28>
A material for forming a film for lithography was formed by using 5 parts by mass of BAPP citraconic maleimide and 2 parts by mass of DABPA-CN as a crosslinking agent, and blending 0.1 part by mass of Irgacure184 (manufactured by BASF corporation) as a photo radical polymerization initiator.
A composition for forming a film for lithography was prepared in the same manner as in example 20.
< example 29>
A film-forming material for lithography was formed by using 5 parts by mass of BAPP citraconic maleimide and 2 parts by mass of BPA-CA as a crosslinking agent, and 0.1 part by mass of Irgacure184 (manufactured by BASF corporation) as a photo radical polymerization initiator.
A composition for forming a film for lithography was prepared in the same manner as in example 20.
< example 30>
A film-forming material for lithography was formed by using 5 parts by mass of BAPP citraconic maleimide and 12 parts by mass of APG-12 as a crosslinking agent, and 0.1 part by mass of Irgacure184 (manufactured by BASF corporation) as a photo radical polymerization initiator.
A composition for forming a film for lithography was prepared in the same manner as in example 20.
< example 31>
A film-forming material for lithography was formed by using 5 parts by mass of BAPP citraconic maleimide and 22 parts by mass of APG-22 as a crosslinking agent, and 0.1 part by mass of Irgacure184 (manufactured by BASF corporation) as a photo radical polymerization initiator.
A composition for forming a film for lithography was prepared in the same manner as in example 20.
< example 32>
A film-forming material for lithography was formed by using 5 parts by mass of BAPP citraconic maleimide and 2 parts by mass of DDM as a crosslinking agent, and 0.1 part by mass of Irgacure184 (manufactured by BASF corporation) as a photo radical polymerization initiator.
A composition for forming a film for lithography was prepared in the same manner as in example 20.
< example 20-2>
A material for forming a film for lithography was prepared by mixing 5 parts by mass of BAPP citraconic maleimide and 0.1 part by mass of WPBG-300 (manufactured by FUJIFILM Wako Pure Chemical Corporation) represented by the following formula as a photobase generator.
To 5 parts by mass of the above-mentioned film-forming material for lithography, 95 parts by mass of PGMEA as a solvent was added, and the mixture was stirred at room temperature for at least 3 hours or more with a stirrer, thereby preparing a film-forming composition for lithography.
Figure BDA0003066334200000631
< examples 21 and 2>
A material for forming a film for lithography was prepared by blending 5 parts by mass of APB-N citraconic maleimide and 0.1 part by mass of WPBG-300 (manufactured by FUJIFILM Wako Pure Chemical Corporation) as a photobase generator.
A composition for forming a film for lithography was prepared in the same manner as in example 20.
< example 22-2>
A material for forming a film for lithography was prepared by compounding 5 parts by mass of HFBAPP citraconmaleimide and 0.1 part by mass of WPBG-300 (manufactured by FUJIFILM Wako Pure Chemical Corporation) as a photobase generator.
A composition for forming a film for lithography was prepared in the same manner as in example 20.
< example 23-2>
A material for forming a film for lithography was prepared by mixing 5 parts by mass of BisAP citraconmaleimide and 0.1 part by mass of WPBG-300 (manufactured by FUJIFILM Wako Pure Chemical Corporation) as a photobase generator.
A composition for forming a film for lithography was prepared in the same manner as in example 20.
< example 24-2>
A material for forming a film for lithography was prepared by blending 5 parts by mass of BMI citraconic maleimide resin and 0.1 part by mass of WPBG-300 (manufactured by FUJIFILM Wako Pure Chemical Corporation) as a photobase generator.
A composition for forming a film for lithography was prepared in the same manner as in example 20.
< example 24A-2>
A material for forming a film for lithography was prepared by mixing 5 parts by mass of a BMI citraconic maleimide high molecular weight polymer and 0.1 part by mass of WPBG-300 (manufactured by FUJIFILM Wako Pure Chemical Corporation) as a photobase generator.
A composition for forming a film for lithography was prepared in the same manner as in example 20.
< example 25-2>
A material for forming a film for lithography was prepared by blending 5 parts by mass of BAN citraconic maleimide resin and 0.1 part by mass of WPBG-300 (manufactured by FUJIFILM Wako Pure Chemical Corporation) as a photobase generator.
A composition for forming a film for lithography was prepared in the same manner as in example 20.
< example 25A-2>
A material for forming a film for lithography was prepared by mixing 5 parts by mass of BAN citraconic maleimide high molecular weight material and 0.1 part by mass of WPBG-300 (manufactured by FUJIFILM Wako Pure Chemical Corporation) as a photobase generator.
A composition for forming a film for lithography was prepared in the same manner as in example 20.
< example 26-2>
A material for forming a film for lithography was formed using 5 parts by mass of BAPP citraconic maleimide and 0.1 part by mass of WPBG-300 (manufactured by FUJIFILM Wako Pure Chemical Corporation) as a photobase generator as a crosslinking agent, together with BF-BXZ 2 parts by mass as a crosslinking agent.
A composition for forming a film for lithography was prepared in the same manner as in example 20.
< example 27-2>
A material for forming a film for lithography was formed by blending 0.1 part by mass of WPBG-300 (manufactured by FUJIFILM Wako Pure Chemical Corporation) as a photobase generator with 5 parts by mass of BAPP citraconic maleimide and 2 parts by mass of NC-3000-L as a crosslinking agent.
A composition for forming a film for lithography was prepared in the same manner as in example 20.
< example 28-2>
A material for forming a film for lithography was formed by compounding 0.1 part by mass of WPBG-300 (manufactured by FUJIFILM Wako Pure Chemical Corporation) as a photobase generator with 5 parts by mass of BAPP citraconic maleimide and 2 parts by mass of DABPA-CN as a crosslinking agent.
A composition for forming a film for lithography was prepared in the same manner as in example 20.
< example 29-2>
A film-forming material for lithography was formed by using 5 parts by mass of BAPP citraconic maleimide and 2 parts by mass of BPA-CA as a crosslinking agent, and 0.1 part by mass of Irgacure184 (manufactured by BASF corporation) as a photo radical polymerization initiator.
A composition for forming a film for lithography was prepared in the same manner as in example 20.
< example 30-2>
A material for forming a film for lithography was prepared by compounding 0.1 part by mass of WPBG-300 (manufactured by FUJIFILM Wako Pure Chemical Corporation) as a photobase generator with 5 parts by mass of BAPP citraconic maleimide and 12 parts by mass of APG-12 as a crosslinking agent.
A composition for forming a film for lithography was prepared in the same manner as in example 20.
< example 31-2>
A material for forming a film for lithography was prepared by compounding 0.1 part by mass of WPBG-300 (manufactured by FUJIFILM Wako Pure Chemical Corporation) as a photobase generator with 5 parts by mass of BAPP citraconic maleimide and 22 parts by mass of APG-22 as a crosslinking agent.
A composition for forming a film for lithography was prepared in the same manner as in example 20.
< example 32-2>
A material for forming a film for lithography was prepared by compounding 0.1 part by mass of WPBG-300 (manufactured by FUJIFILM Wako Pure Chemical Corporation) as a photobase generator with 5 parts by mass of BAPP citraconic maleimide and 2 parts by mass of DDM as a crosslinking agent.
A composition for forming a film for lithography was prepared in the same manner as in example 20.
< preparation of underlayer coating from compositions for Forming photolithographic films of examples 1 to 19 and comparative examples 1 to 10>
The compositions for forming a film for lithography of examples 1 to 19 and comparative examples 1 to 10 having the compositions shown in Table 1 were spin-coated on a silicon substrate, and then baked at 240 ℃ for 60 seconds to measure the film thickness of the coating film. Thereafter, the silicon substrate was immersed in a mixed solvent of PGMEA 70%/PGME 30% for 60 seconds, the adhering solvent was removed by an air duster, and then solvent drying was performed at 110 ℃. The film thickness reduction rate (%) was calculated from the difference in film thickness before and after immersion, and the curability of each underlayer film was evaluated according to the evaluation criteria shown below.
The underlayer coating after curing and baking at 240 ℃ was further baked at 400 ℃ for 120 seconds, and the film thickness reduction rate (%) was calculated from the difference in film thickness before and after baking, and the film heat resistance of each underlayer coating was evaluated according to the evaluation criteria shown below. Then, the etching resistance was evaluated under the conditions shown below.
Further, the burying property and the flatness property into the step substrate were evaluated under the conditions shown below.
< preparation of underlayer coating from compositions for Forming photolithographic films of examples 20 to 32 and examples 20-2 to 32-2>
The compositions for forming a film for lithography of examples 26 to 38 having the compositions shown in Table 2 were spin-coated on a silicon substrate, baked at 150 ℃ for 60 seconds to remove the solvent of the coating film, and then subjected to a high-pressure mercury lamp at a cumulative exposure of 1500mJ/cm2After curing for 60 seconds, the film thickness of the coating film was measured. Thereafter, the silicon substrate was immersed in a mixed solvent of PGMEA 70%/PGME 30% for 60 seconds, the adhering solvent was removed by a pneumatic dust collector, and then solvent drying was performed at 110 ℃. The film thickness reduction rate (%) was calculated from the difference in film thickness before and after immersion, and the curability of each underlayer film was evaluated according to the evaluation criteria described below.
Further, the film was baked at 400 ℃ for 120 seconds, and the film thickness reduction rate (%) was calculated from the difference in film thickness before and after baking, and the film heat resistance of each underlayer film was evaluated according to the evaluation criteria shown below. Then, the etching resistance was evaluated under the conditions shown below.
Further, the burying property and the flatness property into the step substrate were evaluated under the conditions shown below.
[ evaluation of curability ]
< evaluation criteria >
S: the film thickness reduction rate before and after solvent impregnation is less than or equal to 1 percent
A: 1% < the film thickness reduction rate before and after solvent immersion is less than or equal to 5%
B: the film thickness reduction rate before and after solvent immersion is more than 5%
[ evaluation of film Heat resistance ]
< evaluation criteria >
S: the film thickness reduction rate before and after baking at 400 ℃ is less than or equal to 10 percent
A: the film thickness reduction rate before and after baking at the temperature of 10% <400 ℃ is less than or equal to 15%
B: the film thickness reduction rate before and after baking at 15% <400 ℃ is less than or equal to 20%
C: the film thickness reduction rate before and after baking at 400 ℃ is more than 20 percent
[ etching test ]
An etching device: RIE-10NR manufactured by SAMCO International Inc
Output power: 50W
Pressure: 4Pa
Time: 2 minutes
Etching gas
CF4Gas flow rate: o is2Gas flow rate 5: 15(sccm)
[ evaluation of etching resistance ]
The etching resistance was evaluated according to the following procedure.
First, an underlayer film of a novolak resin was formed under the same conditions as in example 1, except that a novolak resin (PSM 4357, manufactured by seiko chemical corporation) was used in place of the material for forming a film for lithography in example 1, and the drying temperature was set to 110 ℃. Then, the etching test described above was performed on the novolac lower layer film, and the etching rate at that time was measured.
Next, the etching tests were carried out in the same manner for the lower layer films of examples 1 to 19 and comparative examples 1 to 10, and the etching rates at these times were measured.
Then, the etching resistance was evaluated according to the following evaluation criteria, using the etching rate of the lower layer film of the novolak as a reference. From the practical viewpoint, the following S evaluation is particularly preferable, and the a evaluation and the B evaluation are preferable.
< evaluation criteria >
S: the etching rate is lower than-30% compared with the lower film of the novolac
A: the etching rate is-30% or more and less than-20% as compared with the lower film of the novolak
B: the etching rate is more than-20% and less than-10% in comparison with the lower layer film of the novolac
C: an etching rate of-10% or more and 0% or less as compared with a lower layer film of a novolak
[ evaluation of embedding Properties of step substrates ]
The evaluation of embeddability into the step substrate was performed according to the following procedure.
The composition for forming an underlayer film for lithography was applied to SiO with a film thickness of 80nm and a line and space width of 60nm2The substrate was baked at 240 ℃ for 60 seconds, thereby forming a 90nm underlayer film. The cross section of the obtained film was cut out and observed with an electron microscope to evaluate embeddability into a step substrate.
< evaluation criteria >
A: SiO with 60nm line width/line distance2The substrate has no defect in the uneven portion and is embedded in the lower layer film.
C: SiO with 60nm line width/line distance2The substrate has a defect in the uneven portion, and the underlying film is not embedded.
[ evaluation of flatness ]
SiO mixed in the trenches with width of 100nm, pitch of 150nm and depth of 150nm (length-width ratio: 1.5) and the trenches with width of 5 μm and depth of 180nm (open space)2The film-forming compositions obtained above were applied to the step substrates, respectively. Then, the resultant was baked at 240 ℃ for 120 seconds in an atmospheric atmosphere to form a film thickness200nm of resist underlayer film. The shape of the resist underlayer film was observed with a scanning electron microscope ("S-4800" by Hitachi High-Technologies Corporation), and the difference (. DELTA.FT) between the maximum value and the minimum value of the film thickness of the resist underlayer film in the trench or space was measured.
< evaluation criteria >
S: delta FT <10nm (best flatness)
A: 10nm or less Δ FT <20nm (good flatness)
B: 20nm ≤ Δ FT <40nm (slightly good flatness)
C: Δ FT of 40nm or less (poor flatness)
[ tables 1-1]
TABLE 1
Figure BDA0003066334200000691
[ tables 1-2]
TABLE 1
Figure BDA0003066334200000701
As is clear from Table 1, it was confirmed that examples 1 to 19 using the composition for forming a film for lithography according to the present embodiment containing citraconimide and citraconimide resin are superior in curability, film heat resistance and etching resistance to citraconimide of comparative examples 3 to 8, and superior in flatness to maleimide of comparative examples 9 to 10. In particular, it was confirmed that both high heat resistance and excellent flatness of the film were achieved by using a BMI citraconic maleimide high molecular weight material or a BAN citraconic maleimide high molecular weight material.
The compositions of examples 1 to 6 and comparative examples 3 to 10 were subjected to a storage stability test at room temperature of 25 ℃ for one month to visually confirm the presence or absence of precipitates. As a result, it was confirmed that the compositions of examples 1 to 6 did not precipitate, but the compositions of comparative examples 3 to 10 did precipitate visually.
Thus, it was confirmed that the composition for forming a film for lithography according to the present embodiment, which contains citraconimide and citraconimide resin, has superior solvent solubility and storage stability compared to citraconimide of comparative examples 3 to 8 and maleimide of comparative examples 9 to 10.
[ Table 2-1]
TABLE 2
Figure BDA0003066334200000711
[ tables 2-2]
TABLE 2
Figure BDA0003066334200000721
< example 33>
The composition for forming a film for lithography in example 1 was coated on SiO with a film thickness of 300nm2The substrate was baked at 240 ℃ for 60 seconds and further at 400 ℃ for 120 seconds to form an underlayer film having a thickness of 70 nm. A resist solution for ArF was applied to the underlayer film, and the film was baked at 130 ℃ for 60 seconds, thereby forming a photoresist layer having a film thickness of 140 nm. As a resist solution for ArF, a compound represented by the following formula (22): 5 parts by mass of triphenylsulfonium nonafluoromethanesulfonate: 1 part by mass and tributylamine: 2 parts by mass and PGMEA: 92 parts by mass were compounded to prepare a solution.
The compound of formula (22) is prepared as follows. Specifically, 4.15g of 2-methyl-2-methacryloxyadamantane, 3.00g of methacryloxy- γ -butyrolactone, 2.08g of 3-hydroxy-1-adamantyl methacrylate, and 0.38g of azobisisobutyronitrile were dissolved in 80mL of tetrahydrofuran to prepare a reaction solution. The reaction solution was polymerized for 22 hours while maintaining the reaction temperature at 63 ℃ under a nitrogen atmosphere, and then the reaction solution was dropwise added to 400mL of n-hexane. The resulting resin thus obtained was solidified and purified, and the resulting white powder was filtered and dried at 40 ℃ under reduced pressure to obtain a compound represented by the following formula.
Figure BDA0003066334200000731
In the formula (22), the numbers 40, 40 and 20 represent the ratios of the respective structural units, and do not represent a block copolymer.
Subsequently, the photoresist layer was exposed to light using an electron beam drawing apparatus (manufactured by Elionix Inc.; ELS-7500, 50keV), baked at 115 ℃ for 90 seconds (PEB), and developed in a 2.38 mass% aqueous solution of tetramethylammonium hydroxide (TMAH) for 60 seconds, thereby obtaining a positive resist pattern. The evaluation results are shown in table 3.
< example 34>
A positive resist pattern was obtained in the same manner as in example 33, except that the composition for forming a lower layer film for lithography in example 2 was used in place of the composition for forming a lower layer film for lithography in example 1. The evaluation results are shown in table 3.
< example 35>
A positive resist pattern was obtained in the same manner as in example 33, except that the composition for forming a lower layer film for lithography in example 3 was used instead of the composition for forming a lower layer film for lithography in example 1. The evaluation results are shown in table 3.
< example 36>
A positive resist pattern was obtained in the same manner as in example 33, except that the composition for forming a lower layer film for lithography in example 4 was used in place of the composition for forming a lower layer film for lithography in example 1. The evaluation results are shown in table 3.
< comparative example 11>
A photoresist layer was formed directly on SiO in the same manner as in example 33, except that formation of an underlayer film was not performed2A positive resist pattern was obtained on the substrate. The evaluation results are shown in table 3.
[ evaluation ]
The shapes of the resulting resist patterns of 55nmL/S (1: 1) and 80nmL/S (1: 1) were observed using an electron microscope (S-4800) manufactured by Hitachi, Ltd., in examples 33 to 36 and comparative example 11, respectively. The shape of the resist pattern after development was evaluated as good if no pattern collapse and good squareness were observed, and as bad if not observed. The results of this observation were evaluated by using the minimum line width, which is free from pattern collapse and has good rectangularity, as an index for evaluation. Further, the minimum electron beam energy at which a good pattern shape can be drawn is used as an index for evaluation.
[ Table 3]
TABLE 3
Figure BDA0003066334200000741
As is clear from table 3, it was confirmed that examples 33 to 36 using the composition for forming a film for lithography according to the present embodiment containing citraconic maleimide and citraconic maleimide resins are significantly superior in both resolution and sensitivity to comparative example 11. Further, it was confirmed that the resist pattern after development had no pattern collapse and had good rectangularity. Further, the difference in the resist pattern shape after development showed that the underlayer films of examples 33 to 36 obtained from the compositions for forming a film for lithography of examples 1,2, 3 and 4 had good adhesion to the resist material.
The present application is based on the japanese patent application No. 2018, 11, 21, incorporated herein by reference (japanese application No. 2018-218042).
Industrial applicability
The material for forming a film for lithography according to the present embodiment has high heat resistance and high solvent solubility, has excellent embedding properties into a step substrate and excellent film flatness, and can be applied to a wet process. Therefore, a composition for forming a film for lithography containing a material for forming a film for lithography can be widely and effectively used in various applications requiring these properties. In particular, the present invention is effectively applicable to the fields of an underlayer film for lithography and an underlayer film for a multilayer resist.

Claims (29)

1. A film-forming material for lithography, comprising: a compound having a group of formula (0A) and a group of formula (0B),
Figure FDA0003066334190000011
in the formula (0B), the metal oxide,
r is independently selected from the group consisting of hydrogen atoms and C1-C4 alkyl groups, wherein at least one R is a C1-C4 alkyl group.
2. The film-forming material for lithography according to claim 1, wherein the compound is represented by formula (1A)0) It is shown that,
Figure FDA0003066334190000012
formula (1A)0) In (1),
r is independently selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 4 carbon atoms, wherein at least one R is an alkyl group having 1 to 4 carbon atoms,
z is a 2-valent group having 1 to 100 carbon atoms, which optionally contains a heteroatom.
3. The film-forming material for lithography according to claim 1 or 2, wherein said compound is represented by formula (1A),
Figure FDA0003066334190000021
in the formula (1A), the compound (A),
r is independently selected from the group consisting of a hydrogen atom and an alkyl group having 1 to 4 carbon atoms, wherein at least one R is an alkyl group having 1 to 4 carbon atoms,
each X is independently selected from the group consisting of a single bond, -O-, -CH2-、-C(CH3)2-、-CO-、-C(CF3)2-, -CONH-and-COO-,
a is selected from the group consisting of a single bond, an oxygen atom, and a divalent group of 1 to 80 carbon atoms optionally containing a hetero atom,
R1each independently a group of carbon number 0 to 30 optionally containing a hetero atom,
m1 is an integer of 0 to 4.
4. The material for forming a film for lithography according to claim 3, wherein A is a single bond, an oxygen atom, - (CH)2)p-、-CH2C(CH3)2CH2-、-(C(CH3)2)p-、-(O(CH2)q)p-、-(O(C6H4))p-, or any of the following structures,
Figure FDA0003066334190000022
y is a single bond, -O-, -CH2-、-C(CH3)2-、-C(CF3)2-、
Figure FDA0003066334190000031
p is an integer of 0 to 20,
q is an integer of 0 to 4.
5. The film-forming material for lithography according to claim 3 or 4, wherein each X is independently a single bond, -O-, -C (CH)3)2-, -CO-, or-COO-,
a is a single bond, an oxygen atom, or the following structure,
Figure FDA0003066334190000032
y is-C (CH)3)2-or-C (CF)3)2-。
6. The film-forming material for lithography according to claim 1 or 2, wherein said compound is represented by formula (2A),
Figure FDA0003066334190000033
in the formula (2A), the compound (A),
r' is independently selected from the group consisting of hydrogen atom and C1-C4 alkyl,
R2each independently a group of carbon number 0 to 10 optionally containing a hetero atom,
m2 is an integer of 0 to 3,
m 2' are each independently an integer of 0 to 4,
n is an integer of 0 to 4,
a plurality of are composed of
Figure FDA0003066334190000041
The group represented comprises at least a group of formula (0A) and a group of formula (0B).
7. The film-forming material for lithography according to claim 1 or 2, wherein said compound is represented by formula (3A),
Figure FDA0003066334190000042
in the formula (3A), the compound (A),
r' is independently selected from the group consisting of hydrogen atom and C1-C4 alkyl,
R3and R4Each independently a group of carbon number 0 to 10 optionally containing a hetero atom,
m3 is an integer of 0 to 4,
m4 is an integer of 0 to 4,
n is an integer of 1 to 4,
a plurality of are composed of
Figure FDA0003066334190000051
The group represented comprises at least a group of formula (0A) and a group of formula (0B).
8. The film forming material for lithography according to any one of claims 2 to 5, wherein the hetero atom is selected from the group consisting of oxygen, fluorine and silicon.
9. The film-forming material for lithography according to any one of claims 1 to 8, further comprising a crosslinking agent.
10. The film forming material for lithography according to claim 9, wherein the crosslinking agent is at least 1 selected from the group consisting of a phenol compound, an epoxy compound, a cyanate ester compound, an amino compound, a benzoxazine compound, a melamine compound, a guanamine compound, a glycoluril compound, a urea compound, an isocyanate compound, and an azide compound.
11. The film-forming material for lithography according to claim 9 or 10, wherein said crosslinking agent has at least 1 allyl group.
12. The film forming material for lithography according to any one of claims 9 to 11, wherein the content ratio of the crosslinking agent is 0.1 to 100 parts by mass, assuming that the mass of the compound is 100 parts by mass.
13. The film-forming material for lithography according to any one of claims 1 to 12, further comprising a crosslinking accelerator.
14. The film forming material for lithography according to claim 13, wherein said crosslinking accelerator comprises at least 1 selected from the group consisting of amines, imidazoles, organophosphines, and lewis acids.
15. The material for forming a film for lithography according to claim 13 or 14, wherein the content ratio of the crosslinking accelerator is 0.1 to 5 parts by mass when the mass of the compound is 100 parts by mass.
16. The film-forming material for lithography according to any one of claims 1 to 15, further comprising a radical polymerization initiator.
17. The material for forming a film for lithography according to claim 16, wherein the radical polymerization initiator contains at least 1 selected from the group consisting of a ketone-based photopolymerization initiator, an organic peroxide-based polymerization initiator and an azo-based polymerization initiator.
18. The material for forming a film for lithography according to claim 16 or 17, wherein a content ratio of the radical polymerization initiator is 0.05 to 25 parts by mass when the mass of the compound is set to 100 parts by mass.
19. A composition for forming a film for lithography, comprising: the film-forming material for lithography and a solvent according to any one of claims 1 to 18.
20. The composition for forming a film for lithography according to claim 19, further comprising an acid generator.
21. The composition for forming a film for lithography according to claim 19 or 20, further comprising an alkaline compound.
22. The composition for forming a film for lithography according to any one of claims 19 to 21, wherein the film for lithography is an underlayer film for lithography.
23. An underlayer film for lithography formed using the composition for forming a film for lithography according to claim 22.
24. A method for forming a resist pattern, comprising the steps of:
a step of forming an underlayer film on a substrate using the composition for forming a film for lithography according to claim 22;
forming at least 1 photoresist layer on the underlayer film; and the combination of (a) and (b),
and a step of irradiating a predetermined region of the photoresist layer with radiation and developing the photoresist layer.
25. A pattern forming method includes the steps of:
a step of forming an underlayer film on a substrate using the composition for forming a film for lithography according to claim 22;
forming an intermediate layer film on the underlayer film using a resist intermediate layer film material containing silicon atoms;
forming at least 1 photoresist layer on the interlayer film;
a step of forming a resist pattern by irradiating a predetermined region of the photoresist layer with radiation and developing the resist pattern;
etching the intermediate layer film using the resist pattern as a mask;
etching the lower layer film using the obtained intermediate layer film pattern as an etching mask; and the combination of (a) and (b),
and a step of forming a pattern on the substrate by etching the substrate using the obtained lower layer film pattern as an etching mask.
26. A purification method comprising the steps of:
a step of dissolving the material for forming a film for lithography according to any one of claims 1 to 18 in a solvent to obtain an organic phase; and the combination of (a) and (b),
a first extraction step of bringing the organic phase into contact with an acidic aqueous solution to extract impurities in the material for forming a film for lithography,
the solvent used in the step of obtaining an organic phase includes a solvent which is not optionally miscible with water.
27. The purification method according to claim 26, wherein the acidic aqueous solution is an aqueous solution of an inorganic acid or an aqueous solution of an organic acid,
the inorganic acid aqueous solution contains 1 or more selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid,
the organic acid aqueous solution contains 1 or more selected from the group consisting of acetic acid, propionic acid, oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid, tartaric acid, citric acid, methanesulfonic acid, phenolsulfonic acid, p-toluenesulfonic acid, and trifluoroacetic acid.
28. The purification process according to claim 26 or 27, wherein the solvent which is not optionally miscible with water is 1 or more solvents selected from the group consisting of toluene, 2-heptanone, cyclohexanone, cyclopentanone, methyl isobutyl ketone, propylene glycol monomethyl ether acetate, and ethyl acetate.
29. The purification method according to any one of claims 26 to 28, further comprising, after the first extraction step: and a second extraction step of bringing the organic phase into contact with water to extract impurities in the material for forming a film for lithography.
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Application publication date: 20210625